A ternary composite for memristor array and preparation method thereof

Abstract

The present invention relates to the technical field of electronic components, and in particular to a ternary complex for a memristor array and a preparation method thereof. The ternary complex comprises A, B and C: A is a guest molecule of a pyridine derivative with an amino terminal, B is a bridging molecule, and C is a main molecule with a cucurbituril structure. A, B and C self-assemble in an aqueous solution through van der Waals forces and hydrophobic interactions between molecules to form a ternary complex; the main molecule C has a barrel-shaped cavity structure, and the barrel-shaped cavity structure encloses the guest molecule A and the bridging molecule B. The ternary complex forms a supramolecular chain junction at the end of a graphene electrode, which can adapt to graphene electrodes with different gaps, greatly improving the molecular connection success rate of the array. The preparation method of the ternary complex is simple, easy to operate, and suitable for large-scale production.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic components, and in particular to a ternary composite material for a memristor array and a preparation method thereof. Background Art

[0002] Memristors are the fourth basic circuit element besides resistors, capacitors, and inductors. Compared with traditional transistors, memristors can simplify circuit design, reduce the use of electronic components, and facilitate integration. Because they have both information storage and computing functions, they are considered to be one of the effective ways to break through the von Neumann bottleneck. However, with the rapid development of technologies such as big data, the Internet, and artificial intelligence, people's demand for memristor storage speed, density, and durability is increasing. The physical size of traditional memristors is difficult to cope with the needs of high-density device development in the future.

[0003] To meet this challenge, single-molecule memristors have emerged as an emerging technology. It combines the characteristics of single-molecule technology and memristors. It not only has the basic functions of memristors, but also exhibits unique performance due to its extremely small size and special material structure. Single-molecule memristors use single molecules as storage units and voltage to regulate the physical and chemical properties of molecules. They have the advantages of memristor miniaturization, low power consumption, and storage and computing integration. In particular, the dynamically breakable single-molecule junction with gold as the electrode realizes the single-molecule storage characteristics. However, for memristors built with breakable single-molecule structures with gold as electrodes, it is difficult to realize large-scale integrated single-molecule memristor arrays. Therefore, it is of great significance to develop a memristor array that can be integrated on a large scale and has non-volatile storage functions. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the related art. To this end, the first object of the present invention is to provide a ternary composite for a memristor array; the second object of the present invention is to provide a method for preparing the ternary composite.

[0005] In order to achieve the first purpose, the technical solution adopted by the present invention is:

[0006] A ternary complex for a memristor array, comprising A, B and C, wherein A is a guest molecule of a pyridine derivative having an amino terminal, B is a bridging molecule, and C is a host molecule having a cucurbituril structure, and A, B and C self-assemble in an aqueous solution through van der Waals forces and hydrophobic interactions between molecules to form a ternary complex;

[0007] The host molecule C has a barrel-shaped cavity structure, and the barrel-shaped cavity structure encloses the guest molecule A and the bridging molecule B;

[0008] When the ternary complex is used in a memristor array, the amino terminal of the A molecule is connected to the carboxyl terminal of the graphene electrode by a covalent bond, and the ternary complex forms a supramolecular chain junction at the end of the graphene electrode.

[0009] Furthermore, the guest molecule A has redox properties, and the ternary complex utilizes the redox properties to switch between high and low resistance states.

[0010] Furthermore, the structural formula of the guest molecule A is or .

[0011] Further, the structural formula of the bridging molecule B is , and Any of .

[0012] Furthermore, the structural formula of the main molecule C is shown below:

[0013] , is 5, 6, 7 or 8.

[0014] Further, the ternary complex is any one of the following structural formulas:

[0015] ; ;

[0016] ;

[0017] n is a repeating unit in the assembly process of A, B and C, and n is a positive integer.

[0018] Furthermore, in the structural formula of the bridging molecule B, R1 is (-CH2) K , K is a positive integer.

[0019] Furthermore, in the structural formula of the bridging molecule B, R3 is any one of S and NH.

[0020] Furthermore, in the structural formula of the bridging molecule B, R2 is any one of H, Cl, Br, CH3, OCH3, SCH3 and NO2.

[0021] In order to achieve the second purpose, the technical solution adopted by the present invention is:

[0022] A method for preparing a ternary composite, for preparing the ternary composite for a memristor array as described in any one of the above items, comprising the following steps:

[0023] S1, dissolving compound B in water to obtain an aqueous solution containing the bridging molecule B;

[0024] S2, dissolving compound C in an aqueous solution containing the bridging molecule B to obtain a mixed solution containing the bridging molecule B and the main molecule C;

[0025] S3, dissolving compound A in the mixed solution, and allowing guest molecule A, bridging molecule B and host molecule C to self-assemble to form a ternary complex solution;

[0026] The ratio of the number of guest molecules A, bridge molecules B and host molecules C is 2:n1:(n1+1), where n1 is a positive integer.

[0027] The above one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects:

[0028] The present invention provides a ternary complex for a memristor array and a preparation method thereof. The main molecule C, the guest molecule A and the bridging molecule B in the ternary complex are self-assembled through van der Waals forces and hydrophobic interactions between molecules. The amino terminal of the guest molecule A is connected to the carboxyl terminal of the graphene electrode by a covalent bond, and the ternary complex forms a supramolecular chain junction at both ends of the graphene electrode. The main molecule C has a barrel-shaped cavity structure, which encloses the guest molecule A and the bridging molecule B, and can adapt to graphene electrodes with different gaps, greatly improving the molecular connection success rate of the array. In addition, the redox characteristics of the guest molecule are utilized to switch between high and low resistance states, thereby realizing the storage function in the ternary complex, and successfully constructing an integrated ternary complex memristor array; the preparation method of the ternary complex provided by the present invention is simple, easy to operate, and suitable for large-scale production.

[0029] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0031] Figure 1 It is a schematic diagram of the three-dimensional structure of the ternary complex provided in an embodiment of the present invention.

[0032] Figure 2 This is a characterization diagram of the ternary complex provided in Example 1 of the present invention.

[0033] Figure 3 This is a characterization diagram of the ternary complex provided in Example 2 of the present invention.

[0034] Figure 4 This is a characterization diagram of the ternary complex provided in Example 3 of the present invention.

[0035] Figure 5 It is a schematic diagram of the structure of the ternary composite memristor array provided in Example 4 of the present invention.

[0036] Figure 6 This is an IV characteristic curve diagram of the ternary composite memristor array provided in Example 4 of the present invention.

[0037] Reference numerals:

[0038] 1. Silicon wafer; 2. Graphene electrode; 3. Gold electrode; 4. Ternary complex; 41. Guest molecule A; 42. Bridging molecule B; 43. Host molecule C. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme of the present invention will be clearly and completely described below in conjunction with the drawings in the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention. The following embodiments are used to illustrate the present invention, but cannot be used to limit the scope of the present invention.

[0040] In the following examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all available from commercial sources unless otherwise specified.

[0041] like Figure 1 As shown, a ternary complex for a memristor array includes A, B and C, A is a guest molecule of a pyridine derivative with an amino terminal, B is a bridging molecule, C is a host molecule with a cucurbituril structure, and the guest molecule A 41, the bridging molecule B 42 and the host molecule C 43 self-assemble in an aqueous solution through van der Waals forces and hydrophobic interactions between molecules to form a ternary complex 4;

[0042] When the ternary complex is used in a memristor array, the amino terminal of the guest molecule A 41 is connected to the carboxyl terminal of the graphene electrode 2 by a covalent bond, and the ternary complex 4 forms a supramolecular chain junction at the end of the graphene electrode 2 .

[0043] The ternary complex is any one of the following structural formulas:

[0044] ; ;

[0045] ;

[0046] n is a repeating unit in the assembly process of A, B and C, and n is a positive integer.

[0047] The dotted box in the molecular structure represents the structural formula of cucurbituril, as shown below:

[0048] , is 5, 6, 7 or 8.

[0049] Example 1 Preparation of ternary complex.

[0050] A ternary complex, the structural formula of which is shown below:

[0051]

[0052] The preparation process of compound A is as follows:

[0053] ;

[0054] In a 250 ml two-necked flask, add 200 ml of acetone, and add 156 mg of compound to the two-necked flask at 20 °C. and 210 mg of I2, and stirred. After the reaction was completed, it was purified by silica gel column chromatography, the solvent was removed by a vacuum pump, and the residue was dried overnight under vacuum to obtain 170 mg of compound With 1.2 g of compound Dissolve in 200 ml of acetonitrile solution, heat to 90°C and reflux for 24 h. After cooling to room temperature, remove the solvent by distillation under reduced pressure, dry the residue under vacuum overnight, and concentrate and purify to obtain compound A. .

[0055] The preparation process of compound B is as follows:

[0056] ;

[0057] Add 84 mg of potassium carbonate to 15 ml of N,N-dimethylformamide solvent, and add 270 mg of compound and 220 mg of compound , with argon as protective gas, heated to reflux at 40°C for 24h. After the reaction was completed, cooled to room temperature, the solvent was removed using a rotary evaporator under vacuum conditions, and the residue was dried overnight to obtain a bridging compound B .

[0058] C is cucurbitac[8]uril, which is commercially available. The molecular structure of cucurbitac[8]uril is shown below:

[0059] ;

[0060] The preparation process of the ternary complex is as follows:

[0061] Weigh 0.26 mg of the compound B prepared above and dissolve it in 10 ml of pure water to prepare a 50 µmol / L solution of compound B. Weigh 1.2 mg of compound C and dissolve it in 5.6 ml of 50 µmol / L solution of compound B to obtain a mixed solution containing B and C;

[0062] 0.15 mg of the compound A molecule prepared above was weighed and dissolved in 5 ml of the mixed solution. Compounds A, B and C can self-assemble to form a ternary complex through van der Waals forces and hydrophobic interactions between molecules. The ratio of the number of molecules of A:B:C in the ternary complex is 2:1:2.

[0063] The isothermal calorimetric titration (ITC) method was used to characterize the ternary complex prepared above, and the binding constants of the C molecule with the A molecule and the B molecule were determined. The specific process is as follows:

[0064] 10 ml of the mixed solution containing A and C prepared above was added to a beaker. The molar concentrations of A and C in the mixed solution were 1 mmol / L and 0.5 mmol / L, respectively. Then, 5 ml of the compound B solution with a concentration of 0.1 mmol / L was measured with a syringe and added dropwise to the beaker. It was observed that the instrument showed an exothermic reaction and as the volume of the bridging molecule B solution added increased, the inclusion of C and B gradually decreased. Among them, the data points were fitted with a single-point model, and the molecular binding constant in the ternary complex was measured to be (1.0±0.1)×10 5 M -1 ,like Figure 2 As shown, the results indicate that the host molecule C includes the guest molecule A and the bridging molecule B within its molecular structure, thereby proving the existence of the ternary complex.

[0065] Example 2 Preparation of ternary complex.

[0066] The molecular structure of the ternary complex is shown below:

[0067] ;

[0068] The preparation process of compound A is the same as that of Example 1.

[0069] The preparation process of compound B is as follows:

[0070] ;

[0071] Under argon atmosphere, add 150 mL of N,N-dimethylformamide and , and 160 mg of CuO, 645 mg of tetrabutylantimony bromide, 3.26 g of Cs2CO3 and 3.92 g of 2-bromoindole were stirred. The reaction mixture was stirred at 145°C for 24 hours. After quenching the reaction with water, it was extracted with ethyl acetate, the organic phase was dried with MgSO4, the solvent was distilled off under reduced pressure, and purified by silica gel column chromatography to obtain compound B.

[0072] C is cucurbitac[8]uril, which is commercially available.

[0073] The preparation process of the ternary complex is as follows:

[0074] Weigh 0.18 mg of the compound B prepared above and dissolve it in 10 ml of pure water to prepare a 50 µmol / L solution of compound B. Weigh 1.2 mg of compound C and dissolve it in 5.6 ml of 50 µmol / L solution B to prepare a mixed solution containing compounds B and C;

[0075] 0.12 mg of compound A was weighed and dissolved in 5 ml of the above mixed solution. Compounds A, B and C self-assembled into a ternary complex through van der Waals forces and hydrophobic interactions between molecules. The molecular ratio of A:B:C in the ternary complex was 2:1:2.

[0076] Isothermal calorimetric titration (ITC) was used to prove that the host molecule C included the guest molecule A and the bridging molecule B, and the binding constants between the host molecule C and the guest molecule A and the bridging molecule B were determined. The specific process is as follows:

[0077] 8 ml of a solution containing compound C and compound A was added to a beaker, where the molar concentrations of compound C and compound A were 1 mmol / L and 0.5 mmol / L, respectively. Then, 6 ml of a 0.1 mmol / L compound B solution was measured with a syringe and added dropwise to the beaker. The instrument displayed an exothermic reaction and as the volume of the added B solution increased, the inclusion of C and B gradually decreased. The data points were fitted with a single-point model, and the molecular binding constant in the ternary complex was measured to be (2.7±0.2)×10 6 M -1 , proving the existence of the ternary complex, proving that the host molecule C encloses the guest molecule A and the bridging molecule B. The results are as follows Figure 3 shown.

[0078] Example 3 Preparation of ternary complex.

[0079] The molecular structure of the ternary complex is shown below:

[0080] ;

[0081] The preparation process of compound A is as follows:

[0082] ;

[0083] 110 mg of the compound and 130 mg of compound Add to a round-bottom flask, add 20 ml of N,N-dimethylformamide and stir the mixture at 110°C for 48 hours. After cooling to room temperature, drop the mixture into ether to obtain the compound Weigh 120 mg of compound Put it into a round-bottom flask, add 10 ml of hydrazine hydrate, 15 ml of ethanol, and 10 ml of N,N-dimethylformamide, and stir the mixture under reflux at 70°C for 2 hours. After the reaction is completed, cool it to room temperature, remove the solvent using a rotary evaporator under vacuum, and dry the residue overnight to obtain the compound .

[0084] The preparation process of compound B is as follows:

[0085] ;

[0086] 170 mg of compound and 865.7mg compound Add to a round-bottom flask and add 20 ml of N,N-dimethylformamide. Stir the mixture at 85°C for 24 hours. After cooling to room temperature, drop the mixture into ether to obtain a white solid. The solvent is removed by filtration, and the solid is washed with ether several times and then vacuum dried to obtain a white powder compound B. .

[0087] C is cucurbitac[8]uril, which is commercially available.

[0088] Weigh 0.3 mg of compound B and dissolve it in 10 ml of pure water to prepare a 50 µmol / L solution of compound B. Weigh 1.2 mg of compound C and dissolve it in 5.6 ml of 50 µmol / L solution of compound B to prepare a mixed solution containing compounds B and C:

[0089] 0.18 mg of compound A was weighed and dissolved in 5 ml of a mixed solution. Compounds A, B and C were able to self-assemble to form a ternary complex through van der Waals forces and hydrophobic interactions between molecules. The molecular ratio of A:B:C in the ternary complex was 2:1:2.

[0090] Isothermal calorimetric titration (ITC) is used to prove that the host molecule C encloses the guest molecule A and the bridging molecule B in the barrel-shaped cavity of the host molecule C, and at the same time determines the molecular binding constant of the ternary complex. The specific process is as follows:

[0091] 10 ml of solution was added to the beaker, in which the molar concentrations of the main molecule C and the guest molecule A were 1 mmol / L and 0.5 mmol / L, respectively. Then, 5 ml of the compound B solution with a molar concentration of 0.1 mmol / L was measured with a syringe and added dropwise to the beaker. The instrument showed an exothermic reaction and as the volume of the compound B solution added increased, the inclusion of the main molecule C and the bridging molecule B gradually decreased. The data points were fitted with a single-point model, and the molecular binding constant of the ternary complex was measured to be (9.1±0.1)×10 4 M -1 , proving the existence of the ternary complex, such as Figure 4 shown.

[0092] Example 4 Preparation of ternary composite memristor array.

[0093] The embodiment of the present invention provides a ternary composite memristor array, and the preparation process thereof is as follows:

[0094] The substrate silicon composed of a silicon dioxide layer and a P-type doped silicon layer was cut into 1×1 cm 2 The silicon wafer 1 was placed in a crystallization dish, and 21 ml of 98% concentrated sulfuric acid and 9 ml of 30% hydrogen peroxide solution were added. The wafer was heated to 120°C, and then ultrasonicated for 5 min and cleaned with ultrapure water. The silicon wafer 1 was dried with nitrogen to obtain a clean silicon wafer 1.

[0095] Cut the copper sheet into 1×8 cm 2 The copper sheet was placed in a chemical vapor deposition (CVD) instrument, and methane and hydrogen were introduced. The temperature was heated to 1050°C and graphene was grown for 1 hour. The grown copper-based graphene was spin-coated with polymethyl methacrylate (PMMA, model: 950 PMMA A6) at a speed of 4000 rpm and baked at 120°C for 2 min. The copper sheet was then cut into 0.8×0.8 cm 2The size was soaked in ferric chloride solution for 2 hours, taken out and repeatedly soaked in dilute hydrochloric acid and ultrapure water solution, and finally placed on silicon wafer 1 to dry. After 12 hours, it was soaked in 40 ml acetone solution and heated to 120°C for about 3 minutes to remove PMMA, thus obtaining silicon wafer 1 covered with a single layer of graphene.

[0096] Place the silicon wafer 1 covered with a single layer of graphene on a coating machine, drop 2 to 3 drops of photoresist (model: AR-P-5350), rotate at a low speed of 2000 rpm for 6 s, then rotate at a speed of 4000 r / s for 40 s, and bake at 110°C for 3 min. Place the device coated with photoresist in the photolithography machine, install the corresponding mask, expose for 2 s at a UV lamp power of 300 W, take it out and soak it in the developer for about 8 s, rinse with ultrapure water and blow dry. Put the developed silicon wafer 1 on the substrate and put it into the vacuum evaporation equipment, and use a vacuum pump to pump the pressure in the chamber to 5×10 -4 Pa, chromium and gold were evaporated to 8 nm and 30 nm respectively at a plating rate of 0.05 angstroms / second. After the evaporation was completed, the sample was taken out and immersed in 30 ml of acetone solution for 5 min. The photoresist and gold except for the required pattern were taken out to obtain a silicon wafer 1 with a pattern.

[0097] Add 2 to 3 drops of photoresist on the silicon wafer 1 with the pattern etched, rotate it at a speed of 4000 r / s for 40 seconds on the photoresist spreader, heat it to 110℃ and bake it for 3 minutes. Then put the sample into the photolithography machine, install the mask with stripe shape, expose it at a power of 300 W for 2 seconds, and immerse it in the developer for about 10 seconds to obtain the silicon wafer 1 with only stripe shape on the photoresist. Then, put the silicon wafer 1 with stripe shape into the oxygen plasma etcher, pass the oxygen flow rate of 20 sccm, adjust the power to 50 W, and remove the excess graphene under the condition of etching time of 50 seconds. Soak the silicon wafer 1 with excess graphene removed in 20ml acetone solution, fish it out and wash it with ultrapure water and blow it dry to obtain the silicon wafer 1 containing stripe-shaped graphene.

[0098] The silicon wafer 1 with strip-shaped graphene was photolithographically processed, 2 to 3 drops of photoresist were added, the wafer was rotated at 4000 r / s for 40 s, and the wafer was placed on a hot plate and baked at 110°C for 3 min. The silicon wafer 1 was placed in a photolithography machine, mounted on a mask in the shape of an electrode, exposed at a power of 300 W for 2 s, and immersed in a developer for about 15 s to obtain a silicon wafer 1 with a vacant electrode shape. The silicon wafer 1 with a vacant electrode shape was attached to the substrate with tape, placed in the chamber of a vacuum evaporation device, and the pressure in the chamber was pumped to 5×10 -4Pa, chromium and gold were evaporated at a plating rate of 0.05 angstroms / second to a thickness of 8 nm and 80 nm, respectively. After the deposition was completed, the sample was taken out and immersed in 40 ml acetone solution for 10 min to remove excess photoresist and gold, thereby obtaining a silicon wafer 1 with an electrode pattern.

[0099] Place the silicon wafer 1 with the electrode pattern on a coating machine, add 2 to 3 drops of PMMA, rotate at a speed of 2000 r / s for 40 s, bake at 120°C for 2 min, then stick the silicon wafer 1 on the sample stage and put it into the electron beam exposure instrument, move the sample stage to a height of 10 mm within the working range of the electron beam gun, turn on the high voltage and set it to 30 kV after vacuuming, find the position of the silicon wafer 1 that needs to be exposed under the pattern of the scanning electron microscope imaging, load the dotted line pattern drawn by the CAD software, and expose after focusing. After the exposure is completed, take out the silicon wafer 1 and immerse it in the developer for about 5 s to obtain the silicon wafer 1 with the electrode.

[0100] The silicon wafer 1 with electrodes is placed in an oxygen plasma etcher, with an oxygen flow rate of 20 sccm, an etching power of 50 W, and an etching time of 5 s. Graphene is etched under oxygen conditions, and carboxyl groups are generated at the ends of graphene. After etching, the silicon wafer 1 with electrodes is placed on the probe station, and the gold electrode 3 is connected to the positive and negative poles of the probe. A source meter (model: Keysight B2901BL) is used to test the conductivity of the silicon wafer 1. The voltage is set to 0.5 V, and the conductivity of each pair of "gold electrode-graphene-gold electrode" is tested. If the current is above picoamperes, the silicon wafer 1 is placed in an oxygen plasma etcher for etching until the test current is displayed below picoamperes, which is a short circuit, and the silicon wafer 1 with graphene electrodes is obtained.

[0101] Taking the ternary complex 4 provided in Example 3 as an example, the step-by-step assembly process of the memristor array is described, and a mixed solution of the bridge molecule B and the main molecule C is prepared: 0.3 mg of compound B is weighed and dissolved in 10 ml of pure water solution to prepare a 50 µmol / L compound B solution. 1.2 mg of compound C is weighed and dissolved in 5.6 ml of a 50 µmol / L compound B solution, and the molar concentrations of compound B and compound C in the mixed solution are 50 µmol / L and 100 µmol / L, respectively.

[0102] The amino terminal of the guest molecule A 41 is assembled onto the graphene electrode 2 with a carboxyl terminal. The process is as follows: Take a 50 ml two-necked bottle, apply vacuum grease to the left mouth, screw the 90° suction joint into the left mouth of the two-necked bottle, and seal it with a sealing film. Fix the two-necked bottle on an iron stand, put the silicon wafer 1 with the graphene electrode 2 into the two-necked bottle, add about 0.5 mg of the amino-terminated compound A, add 0.3 mg of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI), and plug the right mouth of the two-necked bottle with a stopper. Connect the 90° suction joint to the suction pipe of the double-row pipe, turn on the vacuum pump and nitrogen, control the suction for about 3 minutes and the release for about 1 minute three times, and replace the gas in the two-necked bottle until it is filled with nitrogen. Use a syringe to extract 10 ml of anhydrous pyridine (purity of 99%) and inject it into the two-necked bottle. After the injection, connect a balloon filled with nitrogen to the syringe needle and pierce the rubber stopper of the two-necked bottle to ensure that the two-necked bottle is filled with nitrogen and observe the leakage through the size of the balloon. Under the condition of EDCI as a catalyst, the guest molecule A 41 at the amino terminal and the graphene molecule 2 at the carboxyl terminal undergo an amide condensation reaction, and the guest molecule A 41 is covalently bonded to the graphene molecule 2. After standing for 48 hours, the device is fished out, the device is cleaned with acetone and pure water solution, and then blown dry to obtain the graphene electrode 2 assembled with the guest molecule A 41.

[0103] The graphene electrode 2 assembled with the guest molecule A 41 is placed in the mixed solution containing the bridge molecule B 42 and the main molecule C 43 configured as above for the third step of assembly to construct a ternary composite memristor array. The process is as follows: the graphene electrode assembled with the guest molecule A is immersed in the mixed solution containing the compounds B and C for 10 min, and then taken out and immersed in clean water for about 2 s, and dried at 30°C. The guest molecule A 41, the bridge molecule B 42 and the main molecule C 43 can self-assemble to form a ternary composite 4 in a pure aqueous solution through the van der Waals force and hydrophobic interaction between the guest molecule A 41, the bridge molecule B 42 and the main molecule C 43. According to the above concentration ratio, a ternary composite with a ratio of A:B:C molecules of 2:1:2 is obtained, and the preparation of the ternary composite memristor array is completed, as shown in FIG. Figure 5 shown.

[0104] Test the memristor performance of the ternary composite memristor array: At 25°C, place the prepared memristor array on a probe station, which is connected to two sockets (SMU1 and SMU2) of a semiconductor analyzer (model: Keysight B1500A). Two tungsten needles are placed on the gold electrodes 3 on both sides of the memristor array, and the current-voltage module in the semiconductor analyzer is loaded. The scanning voltage is set to the range of -1 V to 1 V, and the performance of the ternary composite is measured, as shown below. Figure 6The IV curve is shown in Figure 2. It is observed that the molecular device has an obvious jump at 0.3 V, which is due to the guest molecule A 41 being reduced to a free radical state, and the device changes from a high resistance state "0" to a low resistance state "1". During the negative voltage scan process, the guest molecule A 41 jumps back from the "1" state to the "0" state, completing the switching of high and low resistance states and realizing the storage function, proving that the prepared ternary composite memristor array has good performance.

[0105] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A ternary composite for a memristor array, characterized in that: It comprises A, B and C, wherein A is a guest molecule of a pyridine derivative having an amino terminal, B is a bridging molecule, and C is a host molecule having a cucurbituril structure, and A, B and C self-assemble in an aqueous solution through van der Waals forces and hydrophobic interactions between molecules to form a ternary complex; Among them, the structural formula of guest molecule A is or ; The structural formula of the bridging molecule B is , and Any of; R1 is (-CH2-) K , K is a positive integer from 1 to 3; R2 is any one of H, Cl, Br, CH3, OCH3, SCH3 and NO2; R3 is any one of S and NH; The host molecule C has a barrel-shaped cavity structure, and the barrel-shaped cavity structure encloses the guest molecule A and the bridging molecule B; When the ternary complex is used in a memristor array, the amino terminal of the guest molecule A is connected to the carboxyl terminal of the graphene electrode by a covalent bond, and the ternary complex forms a supramolecular chain junction at the end of the graphene electrode; Wherein, the ternary complex is any one of the following structural formulas: ； ； ； Represents the structural formula of the main molecule C; n is a repeating unit in the assembly process of A, B and C, and n is an integer greater than or equal to 0.

2. The ternary complex for a memristor array according to claim 1, characterized in that: The structural formula of the main molecule C is shown below: , is 5, 6, 7 or 8.

3. A method for preparing a ternary complex, characterized in that: The method for preparing the ternary composite for a memristor array as claimed in any one of claims 1 to 2 comprises the following steps: S1, dissolving compound B in water to obtain an aqueous solution containing the bridging molecule B; S2, dissolving compound C in an aqueous solution containing the bridging molecule B to obtain a mixed solution containing the bridging molecule B and the main molecule C; S3, dissolving compound A in the mixed solution, and allowing guest molecule A, bridging molecule B and host molecule C to self-assemble to form a ternary complex solution; The ratio of the number of guest molecules A, bridge molecules B and main molecules C is 2:n1:(n1+1), where n1 is a positive integer.

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