Molecular assembly method and application of organic D-A type multi-system conjugated small molecules

Abstract

The invention discloses a molecular assembly method of organic D-A type multi-system conjugated small molecules, which comprises the following steps: by taking 1, 2-diaminobenzene and oxalic acid as raw materials and polyphosphoric acid as a catalyst, carrying out reaction in an alcohol solvent, and after the reaction is finished, separating and purifying to obtain the organic D-A type multi-system conjugated small molecules. Cooling, suction filtration, washing and vacuum drying are performed to prepare a brown powdery solid, namely the organic D-A type multi-system conjugated micromolecule; dispersing the prepared molecular material in an organic solvent, and completely dissolving the molecular material to form a clear and transparent solution to obtain an assembly solution; and dropping the prepared assembly liquid on the surface of clean indium tin oxide glass, standing, and naturally and slowly volatilizing the solvent until the surface of the indium tin oxide glass is dried to obtain the assembly, and the invention provides application of the assembly in ultrahigh-density information storage. The micromolecule material can realize ternary information storage performance, and the prepared assembly can further improve the information storage density of the device and realize ultrahigh-density information storage.

Description

Technical Field

[0001] The invention belongs to the field of functional semiconductor materials and electronic information, and relates to a method for synthesizing and molecular self-assembling an organic DA-type functional small molecule semiconductor material, and its application in the field of ultra-high density information storage. Background Art

[0002] Existing information storage technologies are far from meeting the storage needs, so scientists are developing new technologies to store these massive amounts of data. So far, scientists have proposed two strategies: one is to continuously reduce the size of silicon-based storage units to increase their storage density; the other is to develop multi-bit information storage materials and devices to increase their storage density from 2 to 4. n Improved to 3 n . However, compared with the strategy of reducing the size of storage cells that is highly dependent on physical factors or processing technology, organic multi-level resistive random access memory (ReRAM) devices have attracted increasing attention from scientists over the past decade, mainly due to their diversified processability, simple sandwich structure and ultra-high data storage density (HDSD). Since the first report of ternary memory devices based on small molecule materials in 2010, scientists have developed a series of functional materials to prepare multi-level information storage devices, mainly including small molecule materials, polymer materials, organometallic complex materials, covalent organic framework (COF) materials, as well as transition metal oxide materials, graphene oxide materials, two-dimensional semiconductor materials, perovskite materials, etc.

[0003] Among all the multi-level information storage materials mentioned above, small molecule materials show the best potential in the next generation of ultra-high density information storage materials due to their advantages such as clear structure, simple synthesis, efficient purification, good crystallinity, and excellent scalability. However, multi-level information storage technology based on small molecule materials is still far from practical application. This is mainly because there are still some difficult problems to solve in the small molecule films obtained by processes such as spin coating: first, even for tailor-made small molecule materials, it is difficult to accurately predict the interaction and stacking mode between molecules in the film; second, even if these small molecule films are thermally annealed, the consistency between the internal molecular stacking and the external surface morphology is still not ideal, and there will still be certain crystalline and non-crystalline areas in the film. These problems, in turn, will affect the effective transmission of charge carriers in the film, leading to significant changes in performance between devices and unnecessary reliability failures. Summary of the invention

[0004] Purpose of the invention: The purpose of the present invention is to provide a molecular assembly method for organic DA-type multi-binary conjugated small molecules to overcome the problems of unclear molecular stacking, inconsistent morphology, poor device stability and reproducibility in existing multi-binary memory devices.

[0005] Another object of the present invention is to provide an assembly prepared by a molecular assembly method of organic DA type multi-ary conjugated small molecules for use as an ultra-high density information storage.

[0006] Technical solution: A molecular assembly method of an organic DA-type multi-ary conjugated small molecule of the present invention comprises the following steps: (1) using 1,2-diaminobenzene and oxalic acid as raw materials and polyphosphoric acid as a catalyst to react in an alcohol solvent, and after the reaction is completed, cooling, filtering, washing, and vacuum drying to prepare a brown powder solid, namely an organic DA-type poly-conjugated small molecule, wherein the organic DA-type poly-conjugated small molecule is 6,6'-dinitro-1H,1'H-2,2'-bibenzo[d]imidazole; (2) dispersing the organic DA-type poly-conjugated small molecule obtained in step (1) in an organic solvent, and completely dissolving it by heating, stirring, and ultrasonication to form a clear and transparent solution to obtain an assembly solution; (3) Dropping the assembly liquid prepared in step (2) onto the surface of a clean indium tin oxide glass, leaving it to stand until the solvent evaporates naturally and slowly, until the surface of the indium tin oxide glass is dry, thereby obtaining an assembly.

[0007] Furthermore, in step (1), the 1,2-diaminobenzene is selected from one of 1,2-diamino-4-nitrobenzene, 1,2-diamino-4-nitrobenzene hydrochloride and 1,2-diamino-4-nitrobenzene sulfate; the polyphosphoric acid is selected from one of orthopolyphosphoric acid, isopolyphosphoric acid, oligophosphoric acid and supramolecular polyphosphoric acid; and the alcohol solvent is selected from one of 1,2-ethylene glycol, glycerol, 1,2-propylene glycol, 1,2-butylene glycol and 1,4-butylene glycol.

[0008] Furthermore, in step (1), the molar ratio of 1,2-diaminobenzene to oxalic acid is (2-5):1; and the amount of polyphosphoric acid added is 1%-5% mol of oxalic acid.

[0009] Furthermore, in step (1), the reaction is carried out in an anhydrous and oxygen-free environment, the reaction temperature is 150° C. to 180° C., and the reaction time is 2 h to 5 h.

[0010] Furthermore, in step (1), the filter cake is washed with hot water at 80°C to 100°C for 3 to 5 times.

[0011] Furthermore, in step (2), the organic solvent is selected from one of ethanol, dichloromethane, chloroform, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylformamide.

[0012] Furthermore, in step (2), the concentration of the assembly solution is 10 -5 ~10 -3 mol / L.

[0013] Furthermore, in step (3), the ambient temperature of the ITO glass is 15°C to 30°C.

[0014] The present invention provides a method for synthesizing an organic DA type multi-ary conjugated small molecule by using the above method, and preparing an assembly based on the organic DA type multi-ary conjugated small molecule.

[0015] The present invention provides an application of the above-mentioned assembly as ultra-high density information storage.

[0016] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The synthesis steps of the organic DA-type poly-conjugated small molecules of the present invention are simple and can be obtained in one step. The required raw materials are simple and easy to obtain, and the operation is simple, which is very important for large-scale applications.

[0017] (2) The organic DA type multi-ary conjugated small molecule of the present invention not only introduces two electron-withdrawing groups, nitro and imidazole, into the molecular skeleton, but also introduces NH bonds into the molecular bay area. On the basis of achieving multi-ary conjugation, it can also induce NH...N hydrogen bonding between molecules, which is beneficial to the interaction and close stacking mode of molecules, and ultimately to the free and effective transmission of charge carriers between active layers.

[0018] (3) The self-assembly method of the organic DA-type multi-level conjugated small molecules of the present invention is simple and easy to operate. The configured assembly night is dropped on the glass surface. After the solvent evaporates completely, an assembly of a certain size and morphology can be obtained, thereby improving the consistency of intermolecular stacking.

[0019] (4) The present invention prepares an assembly based on organic DA-type multi-ary conjugated small molecules. Through the electrical performance test of the conductive probe of the conductive atomic force microscope (C-AFM), compared with the commonly used "sandwich" device, its storage unit can be greatly reduced from the micron level to the nanometer level. On the basis of the multi-ary system, the device unit size can be further reduced, further improving the storage density of the information storage device and realizing ultra-high density information storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The figure is a diagram of the synthesis steps of the organic DA type poly-conjugated small molecule in Example 1; Figure 2 This is the nuclear magnetic hydrogen spectrum (1H-NMR) of the organic DA type multi-ary conjugated small molecule in Example 1; Figure 3 Theoretical simulation of the organic DA-type poly-conjugated small molecule in Example 1; Figure 4 This is a SEM image of the assembly formed by molecular self-assembly in Example 18; Figure 5 This is an AFM image of the assembly formed by molecular self-assembly in Example 18; Figure 6 The electrical performance diagram of the assembly prepared in Example 18 measured by conductive atomic force microscopy (C-AFM). DETAILED DESCRIPTION

[0021] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention. Example 1

[0022] The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.41 g of brown powder solid, and its yield was calculated to be about 90%.

[0023] Attached Figure 1 The synthetic route of DA-type poly-conjugated small molecules is shown in Figure 2. Figure 3 The theoretical simulation diagram of DA type multi-conjugated small molecules is shown in the figure. Figure 2 This is the nuclear magnetic resonance hydrogen spectrum (1H-NMR) of the DA-type multi-ary conjugated small molecule material prepared in Example 1. From the 1H-NMR diagram, it can be seen that the nuclear magnetic peak with a δ of 14.49 can be attributed to NH in the molecular bay area, and the peak with a δ of 7.83-8.60 can be attributed to the hydrogen atoms on the aromatic ring; from the theoretical simulation diagram, it can be seen that there are two electron-withdrawing groups of different strengths in the molecular skeleton, and the electron-withdrawing ability of the nitro group is stronger than that of imidazole. Example 2

[0024] The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene hydrochloride (3.98 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.06 g of brown powder solid, and its yield was calculated to be about 77%. Example 3

[0025] The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-ethylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.10 g of brown powder solid, and its yield was calculated to be about 78%. Example 4

[0026] The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.31 g of brown powder solid, and its yield was calculated to be about 86%. Example 5

[0027] The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, oligophosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 1.98 g of brown powder solid, and its yield was calculated to be about 75%. Example 6

[0028] The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 180°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.55 g of brown powder solid, and its yield was calculated to be about 95%. Example 7

[0029] The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 160°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.47 g of brown powder solid, and its yield was calculated to be about 93%. Example 8

[0030] The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 5 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.42 g of brown powder solid, and its yield was calculated to be about 91%. Example 9

[0031] The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 2 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.01 g of brown powder solid, and its yield was calculated to be about 76%.

[0032] Embodiment 10: The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 100°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.22 g of brown powder solid, and its yield was calculated to be about 84%.

[0033] Embodiment 11: The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 90°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.36 g of brown powder solid, and its yield was calculated to be about 89%.

[0034] Embodiment 12: The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed 4 times with 80°C hot water. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.39 g of brown powder solid, and its yield was calculated to be about 90%.

[0035] Embodiment 13: The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (2.52 g, 0.02 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 5 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.35 g of brown powder solid, and its yield was calculated to be about 89%.

[0036] Embodiment 14: The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (6.30 g, 0.05 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.48 g of brown powder solid, and its yield was calculated to be about 94%.

[0037] Embodiment 15: The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, in a nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (3.78 g, 0.03 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 100 mg (3% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at a temperature of 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.45 g of a brown powder solid, and its yield was calculated to be about 92%.

[0038] Embodiment 16: The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, in a nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (3.78 g, 0.03 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 33 mg (1% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at a temperature of 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.10 g of brown powder solid, and its yield was calculated to be about 79%.

[0039] Embodiment 17: The specific steps for the synthesis of organic DA-type poly-conjugated small molecules are as follows: First, under nitrogen atmosphere, 1,2-diamino-4-nitrobenzene (3.78 g, 0.03 mol), oxalic acid (0.90 g, 0.01 mol) and 1,2-propylene glycol (60 ml) were placed in a 100 ml round-bottom flask and stirred evenly, and then 163 mg (5% mol) of the catalyst, orthopolyphosphoric acid, was added. The subsequent reaction was carried out at 150°C for 4 hours. After the reaction was completed, the reaction system was cooled to room temperature, filtered, and then the filter cake was washed with 80°C hot water for 3 times. Finally, the filter cake was placed in a vacuum drying oven and dried for 24 hours to obtain 2.50 g of brown powder solid, and its yield was calculated to be about 94%.

[0040] Embodiment 18: The self-assembly of organic DA-type multi-conjugated small molecules, the specific steps are as follows: First, place the indium tin oxide (ITO) glass in a detergent solution and ultrasonicate it for 30 minutes to remove the oily substances on the surface, then scrub it carefully until there is no obvious particulate contaminant on the glass surface. Secondly, place the cleaned ITO glass in deionized water, acetone and glycerol solvents and ultrasonicate them for 25 minutes each. Finally, blow dry the clean ITO glass with nitrogen in a clean room and place it horizontally in a fume hood for later use.

[0041] Then, a certain amount of organic DA-type poly-conjugated small molecules was weighed and dispersed in 10 ml of tetrahydrofuran solvent to control the concentration to 10 -4 mol / L, and ultrasonically dissolve it completely to form a clear and transparent solution system. Secondly, draw 5 ml of the solution system with a syringe, and then install an organic filter head with a diameter of 0.22 μm on the syringe. Slowly drop this solution system on the surface of the ITO glass until it completely covers the surface of the ITO glass. Control the room temperature at 25°C and wait for it to fully evaporate until the solvent evaporates completely, and then you can get the NH…N hydrogen bond-induced assembly.

[0042] Attached Figure 4 is a SEM image of the assembly formed by the molecular self-assembly of Example 18, attached Figure 4 (a), (b), (c), and (d) are SEM images of the assembly at different pixel sizes. Figure 5 is an AFM image of the assembly formed by the molecular self-assembly of Example 18, Figure 5 (a) is an atomic force microscope image of the assembly, (b) is an atomic force microscope 3D image of the assembly, and (c) is a corresponding thickness image of the assembly. From the images, it can be seen that the molecules self-assemble to form a structure with a regular rectangular morphology.

[0043] Embodiment 19: The self-assembly of organic DA-type multi-conjugated small molecules, the specific steps are as follows: First, place the indium tin oxide (ITO) glass in a detergent solution and ultrasonicate it for 30 minutes to remove the oily substances on the surface, then scrub it carefully until there is no obvious particulate contaminant on the glass surface. Secondly, place the cleaned ITO glass in deionized water, acetone and glycerol solvents and ultrasonicate them for 25 minutes each. Finally, blow dry the clean ITO glass with nitrogen in a clean room and place it horizontally in a fume hood for later use.

[0044] Then, a certain amount of organic DA-type poly-conjugated small molecules was weighed and dispersed in 10 ml of tetrahydrofuran solvent to control the concentration to 10 -5 mol / L, and ultrasonically dissolve it completely to form a clear and transparent solution system. Secondly, draw 5 ml of the solution system with a syringe, and then install an organic filter head with a diameter of 0.22 μm on the syringe. Slowly drop this solution system on the surface of the ITO glass until it completely covers the surface of the ITO glass. Control the room temperature at 25°C and wait for it to fully evaporate until the solvent evaporates completely, and then you can get the NH…N hydrogen bond-induced assembly.

[0045] Embodiment 20: The self-assembly of organic DA-type multi-conjugated small molecules, the specific steps are as follows: First, place the indium tin oxide (ITO) glass in a detergent solution and ultrasonicate it for 30 minutes to remove the oily substances on the surface, then scrub it carefully until there is no obvious particulate contaminant on the glass surface. Secondly, place the cleaned ITO glass in deionized water, acetone and glycerol solvents and ultrasonicate them for 25 minutes each. Finally, blow dry the clean ITO glass with nitrogen in a clean room and place it horizontally in a fume hood for later use.

[0046] Then, a certain amount of organic DA-type poly-conjugated small molecules was weighed and dispersed in 10 ml of tetrahydrofuran solvent to control the concentration to 10 -3 mol / L, and ultrasonically dissolve it completely to form a clear and transparent solution system. Secondly, draw 5 ml of the solution system with a syringe, and then install an organic filter head with a diameter of 0.22 μm on the syringe. Slowly drop this solution system on the surface of the ITO glass until it completely covers the surface of the ITO glass. Control the room temperature at 25°C and wait for it to fully evaporate until the solvent evaporates completely, and then you can get the NH…N hydrogen bond-induced assembly.

[0047] Embodiment 21: The self-assembly of organic DA-type multi-conjugated small molecules, the specific steps are as follows: First, place the indium tin oxide (ITO) glass in a detergent solution and ultrasonicate it for 30 minutes to remove the oily substances on the surface, then scrub it carefully until there is no obvious particulate contaminant on the glass surface. Secondly, place the cleaned ITO glass in deionized water, acetone and glycerol solvents and ultrasonicate them for 25 minutes each. Finally, blow dry the clean ITO glass with nitrogen in a clean room and place it horizontally in a fume hood for later use.

[0048] Then, a certain amount of organic DA-type poly-conjugated small molecules was weighed and dispersed in 10 ml of tetrahydrofuran solvent to control the concentration to 10 -4 mol / L, and ultrasonically dissolve it completely to form a clear and transparent solution system. Secondly, draw 5 ml of the solution system with a syringe, and then install an organic filter head with a diameter of 0.22 μm on the syringe. Slowly drop this solution system on the surface of the ITO glass until it completely covers the surface of the ITO glass. Control the room temperature at 15°C and wait for it to fully evaporate until the solvent evaporates completely, and then you can get the NH…N hydrogen bond-induced assembly.

[0049] Embodiment 22: The self-assembly of organic DA-type multi-conjugated small molecules, the specific steps are as follows: First, place the indium tin oxide (ITO) glass in a detergent solution and ultrasonicate it for 30 minutes to remove the oily substances on the surface, then scrub it carefully until there is no obvious particulate contaminant on the glass surface. Secondly, place the cleaned ITO glass in deionized water, acetone and glycerol solvents and ultrasonicate them for 25 minutes each. Finally, blow dry the clean ITO glass with nitrogen in a clean room and place it horizontally in a fume hood for later use.

[0050] Then, a certain amount of organic DA-type poly-conjugated small molecules was weighed and dispersed in 10 ml of tetrahydrofuran solvent to control the concentration to 10 -4 mol / L, and ultrasonically dissolve it completely to form a clear and transparent solution system. Secondly, draw 5 ml of the solution system with a syringe, and then install an organic filter head with a diameter of 0.22 μm on the syringe. Slowly drop this solution system on the surface of the ITO glass until it completely covers the surface of the ITO glass. Control the room temperature at 30°C and wait for it to fully evaporate until the solvent evaporates completely, and then you can get the NH…N hydrogen bond-induced assembly.

[0051] Embodiment 23: The self-assembly of organic DA-type multi-conjugated small molecules, the specific steps are as follows: First, place the indium tin oxide (ITO) glass in a detergent solution and ultrasonicate it for 30 minutes to remove the oily substances on the surface, then scrub it carefully until there is no obvious particulate contaminant on the glass surface. Secondly, place the cleaned ITO glass in deionized water, acetone and glycerol solvents and ultrasonicate them for 25 minutes each. Finally, blow dry the clean ITO glass with nitrogen in a clean room and place it horizontally in a fume hood for later use.

[0052] Then, a certain amount of organic DA-type poly-conjugated small molecules was weighed and dispersed in 10 ml of ethanol solvent to control the concentration to 10 -4 mol / L, and ultrasonically dissolve it completely to form a clear and transparent solution system. Secondly, draw 5 ml of the solution system with a syringe, and then install an organic filter head with a diameter of 0.22 μm on the syringe. Slowly drop this solution system on the surface of the ITO glass until it completely covers the surface of the ITO glass. Control the room temperature at 25°C and wait for it to fully evaporate until the solvent evaporates completely, and then you can get the NH…N hydrogen bond-induced assembly.

[0053] The assemblies formed by the molecular self-assembly of Examples 19-23 were tested to form structures with regular rectangular morphology.

[0054] Test example: The electrical performance test of conductive atomic force microscopy (C-AFM) is as follows: The prepared ITO glass with regular morphology of Example 18 was placed on the sample stage of Bruker atomic force microscope Nasoscope V Multimode 8, and the conductive probe was mounted on a special conductive needle holder. A forward and reverse scanning voltage of -10 to 10 V was applied to the conductive probe, and its electrical properties were recorded.

[0055] Attached Figure 6 The electrical properties of the assembly were measured by a conductive atomic force microscope (C-AFM). The results show that under a reverse scanning voltage of -10 to 10 V, the assembly exhibits obvious ternary storage performance. At the same time, the tip size of the conductive probe is only about 20 nm, which is much smaller than the 120 μm in the "sandwich" device unit. This invention, based on the realization of multi-base storage, cooperates with the strategy of reducing the size of the device unit to further improve the storage density of the device, and has potential application value.

[0056] Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims

1. A molecular assembly method of organic DA type multi-ary conjugated small molecules, characterized in that: The following steps are involved: (1) using 1,2-diaminobenzene and oxalic acid as raw materials and polyphosphoric acid as a catalyst to react in an alcohol solvent, and after the reaction is completed, cooling, filtering, washing, and vacuum drying to prepare a brown powder solid, namely an organic DA-type poly-conjugated small molecule, wherein the organic DA-type poly-conjugated small molecule is 6,6'-dinitro-1H,1'H-2,2'-bibenzo[d]imidazole; (2) dispersing the organic DA-type poly-conjugated small molecule obtained in step (1) in an organic solvent, and completely dissolving it by heating, stirring, and ultrasonication to form a clear and transparent solution to obtain an assembly solution; (3) Dropping the assembly liquid prepared in step (2) onto the surface of a clean indium tin oxide glass, leaving it to stand until the solvent evaporates naturally and slowly, until the surface of the indium tin oxide glass is dry, thereby obtaining an assembly.

2. The molecular assembly method of organic DA type multi-ary conjugated small molecules according to claim 1, characterized in that: In step (1), the 1,2-diaminobenzene is selected from one of 1,2-diamino-4-nitrobenzene, 1,2-diamino-4-nitrobenzene hydrochloride and 1,2-diamino-4-nitrobenzene sulfate; the polyphosphoric acid is selected from one of orthopolyphosphoric acid, isopolyphosphoric acid, oligophosphoric acid and supramolecular polyphosphoric acid; and the alcohol solvent is selected from one of 1,2-ethylene glycol, glycerol, 1,2-propylene glycol, 1,2-butylene glycol and 1,4-butylene glycol.

3. The molecular assembly method of organic DA type multi-ary conjugated small molecules according to claim 1, characterized in that: In step (1), the molar ratio of 1,2-diaminobenzene to oxalic acid is (2-5):1; and the amount of polyphosphoric acid added is 1%-5% mol of oxalic acid.

4. The molecular assembly method of organic DA type multi-ary conjugated small molecules according to claim 1, characterized in that: In step (1), the reaction is carried out in an anhydrous and oxygen-free environment at a temperature of 150°C to 180°C and a reaction time of 2 h to 5 h.

5. The molecular assembly method of organic DA type multi-ary conjugated small molecules according to claim 1, characterized in that: In step (1), the filter cake is washed with hot water at 80°C to 100°C for 3 to 5 times.

6. The molecular assembly method of organic DA type multi-ary conjugated small molecules according to claim 1, characterized in that: In step (2), the organic solvent is selected from one of ethanol, dichloromethane, chloroform, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylformamide.

7. The molecular assembly method of organic DA type multi-ary conjugated small molecules according to claim 1, characterized in that: In step (2), the concentration of the assembly solution is 10 -5 ~10 -3 mol / L.

8. The molecular assembly method of organic DA type multi-ary conjugated small molecules according to claim 1, characterized in that: In step (3), the ambient temperature of the indium tin oxide glass is 15°C to 30°C.

9. Synthesizing an organic DA-type poly-conjugated small molecule according to the method described in any one of claims 1 to 8, and preparing an assembly based on the organic DA-type poly-conjugated small molecule.

10. Use of the assembly according to claim 9 as ultra-high density information storage.

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