A vertical single-molecule memristor and a preparation method thereof

Abstract

The application provides a vertical monomolecular film memristor and a preparation method thereof. The vertical monomolecular film memristor comprises a substrate, a source electrode, a self-assembled monomolecular film, a drain electrode and a gate electrode which are sequentially arranged on the substrate. The self-assembled monomolecular film comprises a pillar [5] arene molecular system, and a structural formula of the pillar [5] arene molecule is shown as formula A. The self-assembled monomolecular film of the application comprises a pillar [5] arene molecular system with bistability, which is composed of a pillar [5] arene molecule and a silver ion. The pillar [5] arene molecule has a cavity which can accommodate the silver ion. The pillar [5] arene molecular system is applied to the vertical monomolecular film memristor. By adjusting the source-drain voltage or the gate voltage, the silver ion can move in the cavity of the pillar [5] arene molecule, the conversion and adjustment between the high resistance value and the low resistance value are realized, and a vertical monomolecular film memristor with stable structure, high efficiency and adjustable control is obtained.

Description

Technical Field

[0001] This application relates to the field of electronic device technology, and in particular to a vertical monomolecular film memristor and its fabrication method. Background Technology

[0002] With the advent of the artificial intelligence era, the demand for massive data storage and computation is becoming increasingly strong, urgently requiring a low-power, high-speed, and high-capacity storage device. Memristors, as a non-volatile storage technology, offer advantages such as high density, low power consumption, and in-memory computing capabilities, and can simulate some basic characteristics of neurons. Utilizing the characteristics of memristors to construct memory allows data to be retained even when the power is off, and their small size makes them suitable to replace existing flash memory. Furthermore, memristor arrays can be applied to neural network computing, accelerating the progress of artificial intelligence.

[0003] Molecular memristors, integrating in-memory computing, can overcome the time and energy costs associated with the von Neumann bottleneck, providing a powerful solution for efficient, scalable, and universal information processing systems. Therefore, developing a structurally stable and tunable molecular film memristor is essential. Summary of the Invention

[0004] The purpose of this application is to provide a vertical monomolecular film memristor and its fabrication method, so as to obtain a structurally stable and tunable vertical monomolecular film memristor. The specific technical solution is as follows:

[0005] The first aspect of this application provides a vertical monomolecular memristor, which includes a substrate, a source electrode, a self-assembled monomolecular film, a drain electrode, and a gate electrode sequentially disposed on the substrate; the self-assembled monomolecular film includes a columnar aromatic hydrocarbon molecular system, which is composed of columnar aromatic hydrocarbon molecules and silver ions, and the structural formula of the columnar aromatic hydrocarbon molecule is shown in Formula A:

[0006]

[0007] Where n is 5; R1 is selected from hydrogen or methyl, R2 is selected from the groups shown in Formulas I-IV below, and m is an integer from 1 to 10;

[0008]

[0009] The R2 group in the columnar aromatic hydrocarbon molecule is connected to the source electrode by a chemical bond, and the R1 group in the columnar aromatic hydrocarbon molecule is connected to the drain electrode by van der Waals forces.

[0010] In some embodiments of this application, the columnar aromatic molecule is selected from compounds represented by formulas A1-A8:

[0011]

[0012] In some embodiments of this application, the self-assembled monolayer is obtained by self-assembly of a columnar aromatic hydrocarbon molecular system on the source electrode; the molar ratio of columnar aromatic hydrocarbon molecules to silver ions is 1:0.5-1.

[0013] In some embodiments of this application, the source material is selected from Au, Ag, or Pt; the chemical bond is selected from covalent or coordinate bonds; R2 in the columnar aromatic molecule is selected from formula I, the chemical bond is a coordinate bond, and the coordinate bond is a coordinate bond formed between the pyridinyl group and the source; or R2 in the columnar aromatic molecule is selected from formula II, the chemical bond is a covalent bond, and the covalent bond is a C-Au bond, a C-Ag bond, or a C-Pt bond; or R2 in the columnar aromatic molecule is selected from formula III, the chemical bond is a covalent bond, and the covalent bond is an S-Au bond, a S-Ag bond, or a S-Pt bond; or R2 in the columnar aromatic molecule is selected from formula IV, the chemical bond is a coordinate bond, and the coordinate bond is a coordinate bond formed between the amino group and the source.

[0014] In some embodiments of this application, the drain material is selected from graphene; the gate is an ionic liquid gate.

[0015] In some embodiments of this application, the substrate includes a substrate bottom layer and an oxide layer, wherein the substrate bottom layer is made of silicon, mica or sapphire, and the oxide layer is made of silicon dioxide, hafnium dioxide or aluminum oxide.

[0016] In some embodiments of this application, the thickness of the self-assembled monolayer is 0.7 nm-3 nm; the thickness of the source electrode is 50 nm-90 nm; and the thickness of the drain electrode is 0.3 nm-3 nm.

[0017] A second aspect of this application provides a method for fabricating a vertical monomolecular film memristor according to any of the foregoing embodiments, comprising the following steps:

[0018] (1) A blind hole is formed on the substrate, with the bottom of the blind hole exposed on the substrate bottom layer;

[0019] (2) Set the source electrode in the blind hole;

[0020] (3) The columnar aromatic molecules are self-assembled on the source electrode, and silver ions are introduced by adding silver trifluoroacetate solution to obtain a self-assembled monolayer.

[0021] (4) A drain electrode is set on a self-assembled monolayer;

[0022] (5) A gate is set on the drain to obtain a vertical monomolecular memristor.

[0023] The beneficial effects of this application are:

[0024] This application provides a vertical monomolecular memristor and its fabrication method. The vertical monomolecular memristor includes a substrate, a source electrode, a self-assembled monomolecular film, a drain electrode, and a gate electrode sequentially disposed on the substrate. The self-assembled monomolecular film comprises a columnar aromatic hydrocarbon molecular system, the structural formula of which is shown in Formula A. R2 in the columnar aromatic hydrocarbon molecule is chemically bonded to the source electrode, and R1 in the columnar aromatic hydrocarbon molecule interacts with the drain electrode through van der Waals forces, forming a vertical monomolecular structure. The self-assembled monomolecular film of this application comprises a bistable columnar aromatic hydrocarbon molecular system, which is composed of columnar aromatic hydrocarbon molecules and silver ions. Columnar aromatic hydrocarbon molecules are cylindrical molecules with cavities that can accommodate silver ions. By applying the columnar aromatic hydrocarbon molecular system to the vertical monomolecular memristor, the silver ions can move up and down within the cavities of the columnar aromatic hydrocarbon molecules by adjusting the source-drain voltage or the gate voltage, achieving switching control between high and low resistance values, thereby obtaining a structurally stable, efficient, and tunable vertical monomolecular memristor.

[0025] Of course, implementing any product or method of this application does not necessarily require achieving all of the advantages described above at the same time. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other embodiments can be obtained based on these drawings.

[0027] Figure 1 This is a three-dimensional structural schematic diagram of a vertical monomolecular membrane memristor in some embodiments of this application;

[0028] Figure 2 The IV characteristic curve of the vertical monomolecular memristor in Example 1;

[0029] Figure 3 The IV characteristic curve of the vertical monomolecular memristor in Example 1 was measured after being placed in a room temperature and air environment for 7 days. Detailed Implementation

[0030] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art based on this application are within the scope of protection of this application.

[0031] The first aspect of this application provides a vertical monomolecular memristor, such as Figure 1As shown, the vertical monomolecular memristor 100 includes a substrate 10, a source 20, a self-assembled monomolecular film 30, a drain 40, and a gate 50 sequentially disposed on the substrate 10; the self-assembled monomolecular film 30 includes a columnar aromatic hydrocarbon molecular system, which is composed of columnar aromatic hydrocarbon molecules and silver ions, and the structural formula of the columnar aromatic hydrocarbon molecule is shown in Formula A:

[0032]

[0033] Where n is 5; R1 is selected from hydrogen or methyl, R2 is selected from the groups shown in Formulas I-IV below, and m is an integer from 1 to 10;

[0034]

[0035] In the columnar aromatic hydrocarbon molecule, group R2 is chemically bonded to the source electrode, while group R1 interacts with the drain electrode via van der Waals forces. The self-assembled monolayer of this application comprises a bistable columnar aromatic hydrocarbon molecule system, composed of columnar aromatic hydrocarbon molecules and silver ions. Columnar aromatic hydrocarbon molecules are cylindrical molecules with cavities that can accommodate silver ions. By applying this system to a vertical monolayer memristor, the movement of silver ions within the cavities of the columnar aromatic hydrocarbon molecules can be controlled by adjusting the source-drain voltage or gate voltage, enabling the switching between high and low resistance values. This results in a structurally stable, efficient, and tunable vertical monolayer memristor.

[0036] In some embodiments of this application, the columnar aromatic molecule is selected from compounds represented by formulas A1-A8:

[0037]

[0038] The compounds shown in formulas A1-A8 above are cylindrical molecules with cavities that can accommodate silver ions. By applying the columnar aromatic molecule system within the above range to a vertical monomolecular memristor, the movement of silver ions within the cavity of the columnar aromatic molecule can be achieved by adjusting the source-drain voltage or gate voltage. This allows for the switching and control between high and low resistance values, resulting in a structurally stable, efficient, and tunable vertical monomolecular memristor.

[0039] In some embodiments of this application, the self-assembled monolayer is obtained by self-assembling a columnar aromatic hydrocarbon molecular system on the source electrode; the molar ratio of columnar aromatic hydrocarbon molecules to silver ions is 1:0.5-1. By controlling the molar ratio of columnar aromatic hydrocarbon molecules to silver ions within the above range, it is beneficial to control the vertical movement of silver ions within the cavity of the columnar aromatic hydrocarbon molecules, achieving the switching control between high and low resistance values, thereby obtaining a structurally stable, efficient, and tunable vertical monolayer memristor.

[0040] In some embodiments of this application, the source electrode material is selected from Au, Ag, or Pt; the chemical bond is selected from covalent or coordinate bonds; R2 in the columnar aromatic molecule is selected from formula I, and the chemical bond is a coordinate bond, specifically a coordinate bond formed between the pyridinium group and the source electrode. For example, when the source electrode material is Au, the coordinate bond formed between the pyridinium group and the source electrode is... Alternatively, R2 in the columnar aromatic molecule can be selected from formula II, with a covalent bond, specifically a C-Au, C-Ag, or C-Pt bond; or R2 in the columnar aromatic molecule can be selected from formula III, with a covalent bond, specifically an S-Au, S-Ag, or S-Pt bond; or R2 in the columnar aromatic molecule can be selected from formula IV, with a coordinate bond, specifically a coordinate bond formed between the amino group and the source electrode. For example, when the source electrode material is Au, the coordinate bond formed between the amino group and the source electrode is H2N→Au. The self-assembled monolayer self-assembles on the source electrode through the above chemical bonds, resulting in a vertical monolayer memristor with the aforementioned characteristics, exhibiting good stability.

[0041] In some embodiments of this application, the drain material is selected from graphene; the gate is an ionic liquid gate. The ionic liquid gate can improve the stability and control efficiency of the vertical monolayer memristor. Because graphene has extremely high permeability to electric fields and selective permeability to electrons, the double-layer gate voltage formed by the ionic liquid gate can pass vertically downward through the graphene to control the self-assembled monolayer. Meanwhile, the anions and cations in the ionic liquid are isolated by the graphene and will not pass through the graphene to erode the self-assembled monolayer, thereby further improving the stability and control efficiency of the vertical monolayer memristor.

[0042] This application does not impose any particular restrictions on the type of ionic liquid used as the ionic liquid gate, as long as it can achieve the purpose of this application. For example, the ionic liquid can be diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imine (DEME-TFSI) ionic liquid.

[0043] In some embodiments of this application, the substrate includes a substrate bottom layer and an oxide layer. The substrate bottom layer is made of silicon, mica, or sapphire, and the oxide layer is made of silicon dioxide, hafnium dioxide, or aluminum oxide. This application does not impose any particular limitation on the thickness of the substrate, substrate bottom layer, and oxide layer, as long as the purpose of this application can be achieved. For example, the thickness of the substrate is 300 μm-700 μm, and the thickness of the oxide layer is 100 nm-300 nm.

[0044] In some embodiments of this application, the thickness of the self-assembled monolayer is 0.7 nm-3 nm; the thickness of the source electrode is 50 nm-90 nm; and the thickness of the drain electrode is 0.3 nm-3 nm. By controlling the thickness of the self-assembled monolayer, the thickness of the source electrode, and the thickness of the drain electrode within the above ranges, a structurally stable, efficient, and tunable vertical monolayer memristor can be obtained.

[0045] In this application, the source electrode has an atomically flat surface. An atomically flat surface on the source electrode facilitates the formation of self-assembled monolayers to create a structurally stable vertical monolayer memristor, resulting in high stability and gate control efficiency. In this application, "atomic-level flatness" refers to the flatness of the material surface at the atomic level.

[0046] A second aspect of this application provides a method for fabricating a vertical monomolecular film memristor according to any of the foregoing embodiments, comprising the following steps:

[0047] (1) A blind hole is formed on the substrate, with the bottom of the blind hole exposed on the substrate bottom layer;

[0048] (2) Set the source electrode in the blind hole;

[0049] (3) The columnar aromatic molecules are self-assembled on the source electrode, and silver ions are introduced by adding silver trifluoroacetate solution to obtain a self-assembled monolayer.

[0050] (4) A drain electrode is set on a self-assembled monolayer;

[0051] (5) A gate is set on the drain to obtain a vertical monomolecular memristor.

[0052] The preparation method provided in the second aspect of this application can produce a structurally stable, efficient, and tunable vertical monomolecular memristor.

[0053] Prior to step (1) above, the following steps may also be included: pre-treating the substrate to clean its surface, making it clean and free of contaminants. Exemplarily, the pre-treatment may include, but is not limited to, the following steps: ultrasonically cleaning the substrate in a piranha solution for 20-40 minutes. The piranha solution is obtained by mixing 35% H2O2 and concentrated sulfuric acid in a volume ratio of 3:7.

[0054] Before step (1) above, and before cleaning the surface of the substrate, the following steps may be included: depositing a metal gate electrode on the oxide layer of the substrate using a mask, ultraviolet lithography, or deposition technology for external gate test sites. The deposition technology includes electron beam evaporation deposition, atomic layer deposition, or vacuum evaporation deposition. In this application, the metal gate electrode is ring-shaped, and may include, but is not limited to, circular rings, square rings, etc.

[0055] In step (1) above, the substrate includes a substrate bottom layer and an oxide layer. A blind hole penetrating the oxide layer is formed on the substrate, such that the bottom of the blind hole is exposed on the substrate bottom layer, and the source electrode is in direct contact with the substrate bottom layer. This application does not have any particular limitation on the shape of the blind hole. For example, it can be a circular blind hole or a square blind hole, as long as it can achieve the purpose of this application. This application does not have any particular limitation on the method of setting the blind hole, as long as it can achieve the purpose of this application. For example, the method of setting the blind hole may include, but is not limited to, the following steps: setting photoresist on the oxide layer of the substrate, and then using a mask, ultraviolet lithography and buffered oxide etchant (BOE) to etch the oxide layer on the substrate corresponding to the mask, thereby obtaining the blind hole.

[0056] In step (2) above, the source electrode is directly disposed within the blind hole and in direct contact with the bottom layer of the substrate. This application does not impose any particular limitation on the method of disposing of the source electrode, as long as it can achieve the purpose of this application. For example, the method of disposing of the source electrode may include, but is not limited to, the following steps: depositing the source electrode material at the bottom of the blind hole using electron beam evaporation, atomic layer deposition, or thermal evaporation to obtain the source electrode.

[0057] In step (3) above, this application does not impose any particular limitation on the preparation method of the self-assembled monolayer. For example, it may include, but is not limited to, the following steps: dissolving columnar aromatic hydrocarbon molecules in an organic solvent to prepare a solution containing columnar aromatic hydrocarbon molecules with a concentration of 0.1 mmol / L-10 mmol / L; immersing the semi-finished device with the source electrode in the above solution for 4 h-12 h, then immersing it in a silver trifluoroacetate aqueous solution with a concentration of 0.1 mmol / L-10 mmol / L for 4 h-12 h, washing and drying it to form a self-assembled monolayer on the source electrode. This application does not impose any particular limitation on the organic solvent, as long as it can achieve the purpose of this application. For example, the organic solvent is selected from at least one of anhydrous ethanol, propylene carbonate and 1,2,4-trichlorobenzene.

[0058] In step (4) above, the drain covers the blind hole opening and is disposed on the self-assembled monolayer and tightly bonded to it. The drain is prepared in advance and then transferred to the self-assembled monolayer. This application does not impose any particular restrictions on the preparation method of the drain, as long as it can achieve the purpose of this application. When the material of the drain is monolayer graphene, the preparation method of the drain may include, but is not limited to, the following steps: depositing and growing a graphene film on a copper foil, setting photoresist on the graphene film, drying to obtain a multilayer structure of "photoresist layer / graphene film / copper foil / graphene film", then etching to remove the outer graphene film to obtain a three-layer structure of "photoresist layer / graphene film / copper foil", then placing it in a ferric chloride solution to dissolve the copper foil, transferring it to clean deionized water, washing the residual ferric chloride in the graphene to obtain the "photoresist layer / graphene film" structure, transferring it to the surface of the self-assembled monolayer, removing the photoresist layer, and then removing the graphene outside the drain by ultraviolet lithography to obtain the drain. The copper foil used is any copper foil known in the art, and this application does not limit its use. For example, the copper foil is Cu(111) foil. The deposition and growth method of the graphene film may include, but is not limited to, chemical vapor deposition. The photoresist layer is any conventional photoresist layer known in the art, such as, but not limited to, polymethyl methacrylate (PMMA) or polydimethylsiloxane (PDMS). This application does not limit its use, as long as the purpose of this application is achieved. The ferric chloride solution is an aqueous solution of ferric chloride. This application does not have a particular limitation on the mass concentration of the ferric chloride solution, as long as the purpose of this application is achieved. For example, the mass concentration of the ferric chloride solution is 10%-50%, and the pH is 3±0.1. This application does not specifically limit the method for transferring the "photoresist layer / graphene film" structure to the surface of a self-assembled monolayer. For example, it may include, but is not limited to, the following steps: The "photoresist layer / graphene film" structure is sequentially immersed in six hydrochloric acid solutions with decreasing concentration gradients for cleaning; then soaked in deionized water for 15-45 minutes before being removed; next, it is placed in isopropanol solvent to remove water; a semi-finished device with a self-assembled monolayer is used to remove the "photoresist layer / graphene film" structure from the isopropanol solvent; and the solvent is allowed to evaporate naturally, allowing the graphene film to adhere smoothly to the surface of the self-assembled monolayer. Exemplarily, the volume fractions of the five hydrochloric acid solutions with decreasing concentration gradients can be 1%, 0.5%, 0.1%, 0.05%, and 0.01%, respectively.

[0059] Before step (5) above, the following steps may also be included: using a mask, ultraviolet lithography, and deposition techniques to set a metal drain electrode at a position of 2μm-6μm at the opening of the blind hole, for externally introducing graphene drain electrode test sites. The above deposition techniques include electron beam evaporation deposition, atomic layer deposition, or vacuum evaporation deposition.

[0060] In step (5) above, the ionic liquid can be added dropwise onto the drain to form the gate. This application does not have any particular limitation on the amount of ionic liquid added, as long as it can cover the drain.

[0061] Optionally, an adhesion layer can be selectively disposed between the source electrode and the substrate to improve the adhesion between the source electrode and the substrate, thereby improving the structural stability of the vertical monolayer memristor. This application does not impose any particular limitation on the material of the adhesion layer, as long as it achieves the purpose of this application. For example, the material of the adhesion layer may include, but is not limited to, at least one of Ti and Cr. This application does not impose any particular limitation on the thickness of the adhesion layer, as long as it achieves the purpose of this application. For example, the thickness of the adhesion layer is 5 nm-15 nm.

[0062] Test methods and equipment:

[0063] The hydrogen NMR spectrum of the compound was determined using a nuclear magnetic resonance spectrometer.

[0064] The IV characteristic curves of the vertical monomolecular film memristors were tested using a semiconductor parameter analyzer (Agilent B2900). Electrical tests: At room temperature, with a source-drain voltage range of -1V to 1V applied, the current (I) versus source-drain voltage (V) characteristic curves of the vertical monomolecular film memristors prepared in each embodiment were measured, as well as the IV characteristic curves of the vertical monomolecular film memristors after being placed at room temperature for 7 days. The on / off rectification ratio of the vertical antimolecular film memristors in each embodiment was calculated. In the IV characteristic curves of the vertical monomolecular film memristors, the maximum current in the low-resistance state is the on-state current I. max I max At the corresponding voltage, the current in the high-resistance state is I0, and the on / off rectification ratio is equal to I. max / I0. I max The larger the value of / I0, the stronger the tunability of the vertical monomolecular memristor. Figure 2 The IV characteristic curves of the vertical monomolecular film memristor prepared in Example 1 are shown. Furthermore, the IV characteristic curves of the vertical monomolecular film memristor prepared in Example 1 after being placed in air at room temperature for 7 days are shown below. Figure 3 As shown.

[0065] There are no particular limitations on the synthesis method of the compounds in this application; methods known to those skilled in the art can be used for synthesis. The following examples illustrate the synthesis process of the compounds in this application.

[0066] Synthesis Examples

[0067] The reaction processes in the synthesis examples of this application were all carried out under a nitrogen atmosphere. The raw materials used in the synthesis examples are all chemical raw materials well-known to those skilled in the art.

[0068] Synthesis Example 1: Synthesis of Compound A1

[0069]

[0070]

[0071] <Preparation of Intermediate M1>

[0072] 4-Methoxyphenol (B1, 40 mmol) was dissolved in acetone (100 mL) at room temperature, and potassium carbonate (60 mmol) was added with stirring. The resulting solution was stirred for 30 minutes, and then benzyl bromide (4.76 mL, 40 mmol) was added. The mixture was then heated to reflux. The reaction was stirred under reflux for 24 h, cooled to room temperature, filtered, and the solvent was removed by vacuum distillation. The crude product was then extracted with dichloromethane (DCM). The crude product was purified by column chromatography, eluting with a mixture of DCM and n-hexane in a volume ratio of 60:40, to give a white solid, compound B2, in 90% yield.

[0073] Compound B2 (20.0 mmol) was dissolved in anhydrous dichloroethane (40 ml) under a nitrogen atmosphere, and then paraformaldehyde ((CH2O) was added. n The solution was stirred at room temperature for 30 minutes with 60 mmol of boron trifluoride diethyl ether complex (BF3OEt2, 2.5 ml, 20 mmol) at room temperature. Then, methanol (50 ml) was added, and the solution was concentrated and dissolved in DCM (100 ml). The solution was then washed with NaHCO3 aqueous solution (2 × 50 ml) and deionized water (50 ml), dried over anhydrous Na2SO4, concentrated under reduced pressure, and purified by silica gel chromatography. The solution was eluted with a mixture of DCM and n-hexane at a volume ratio of 60:40 to give compound B3 in 10% yield.

[0074] Compound B3 was dissolved in anhydrous ethyl acetate (30 ml), and 10 mg of Pd / C was added (based on the total mass of Pd / C, the mass percentage of Pd was 2%). The mixture was then placed in a catalytic hydrogenation reactor (model bylx-2202, provided by Tianjin Beiyang Lixing Technology Co., Ltd.), and after evacuation, it was filled with H2. The reaction was carried out for 30 min to allow compound B3 to absorb the theoretical amount of hydrogen. The Pd / C catalyst was removed by filtration, and the mixture was then washed with ethyl acetate and methanol. The filtrates from the washings were mixed and evaporated to obtain intermediate M1, which was a white solid.

[0075] <Preparation of intermediate M2>

[0076] Intermediate M1 (5.3 mmol) was dissolved in 20 mL of DCM and transferred to a single-necked round-bottom flask. The mixture was cooled to 0 °C, and triethylamine (Et3N, 5.3 mmol) was added with stirring. Then, methanesulfonyl chloride (CH3ClO2S, 5.3 mmol) was added dropwise while stirring continued. The mixture was stirred at -15 °C for 90 min. The reaction was terminated with HCl solution (1 mol / L, 2 mL), and the solution was washed with saturated aqueous solution of NaHCO3. The organic phase was extracted and washed three times with deionized water. The organic phase was dried with Na2SO4, and the solvent was removed under reduced pressure using a rotary evaporator to obtain intermediate M2.

[0077] <Preparation of Compound A1>

[0078] Sodium tert-butoxide (t-BuONa, 2.67 mmol) and 4-n-propanolpyridine (2.67 mmol) were added to an acetonitrile (CH3CN, 10 mL) solution of M2 (2.8 mmol). The mixture was stirred and heated at 80 °C for 16 hours. After cooling, the solid was filtered, and the filtrate was concentrated. The residue was purified by normal-phase chromatography, eluting with a mixture of ethyl acetate and heptane in a volume ratio of 15:85. The crude mixture was dissolved in ethyl acetate, washed with NaOH (1 mol / L), and the solvent was removed by distillation. The crystals yielded compound A1.

[0079] NMR data for compound A1:

[0080] 1H NMR(400MHz, CDCl3 / DMSO) δ8.50(dt,J=6.0,1.2Hz,10H),7.44–7.37(m,2H),7.38–7.24(m,8H),6.89–6.79(m,4H),6.81–6.6 8(m,6H),4.44–4.31(m,11H),3.90(t,J=1.0Hz,2H),3.87–3.74(m,20H),3.73(t,J=1.0Hz,2H),2.98(td,J=6.4,0.9Hz,10H).

[0081] 13C NMR(100MHz,Chloroform-d)δ152.92,152.90,152.89,152.87,152.86,151.61,151.60,149.34,146.77, 146.76,146.75,146.74,146.73,128.90,128.87,128.84,128.82,128.79,128.77,128.74,128.72,128.6 8,128.67,123.63,123.59,115.04,115.02,115.00,114.98,114.96,113.00,112.98,112.96,112.95,112.93,70.42,70.39,70.36,70.33,70.29,55.74,55.73,55.72,35.53,31.63,31.61,31.59,31.56,30.35.

[0082] Synthesis Example 2: Synthesis of Compound A2

[0083]

[0084] The preparation of intermediate M1 is the same as in synthesis example 1.

[0085] <Preparation of intermediate M3>

[0086] Intermediate M1 (10 mmol) and 1,7-dibromopropane (80 mmol) were added to a mixed solvent of CH3CN (30 ml) and anhydrous potassium carbonate (40 mmol); the reaction mixture was refluxed and stirred in an oil bath for 10 hours; potassium carbonate was removed by suction filtration and solvent was removed under reduced pressure; the crude residue was purified by column chromatography to obtain intermediate M3.

[0087] <Preparation of Compound A2>

[0088] Lithium tert-butoxide (t-BuOLi, 0.45 mmol) and 4-dimethylaminopyridine (DMAP, 0.24 mmol) were added to a 10 mL reaction tube under a nitrogen atmosphere and mixed. Then, dimethyl sulfoxide (DMSO, 1.5 mL), hexamethyldimethylformane (0.42 mmol), and intermediate M3 (0.3 mmol) were added sequentially to the reaction tube. The mixture was then stirred in an oil bath at 80 °C for 1 hour. The reaction mixture was filtered through a chromatography column to remove insoluble precipitates. The crude product was then purified by silica gel column chromatography (petroleum ether (PE) to ethyl acetate (EA) volume ratio 100:1) to obtain compound A2.

[0089] NMR data for compound A2:

[0090] 1 H NMR (400MHz, CDCl3 / DMSO) δ6.65(t,J=1.0Hz,6H),6.57(t,J=1.0Hz,6H),4.01–3.90(m,24 H), 3.69 (d, J = 1.1Hz, 13H), 1.96 (t, J = 6.0Hz, 11H), 1.77 (p, J = 6.0Hz, 12H), 1.55 (s, 39H).

[0091] 13 C NMR(100MHz,Chloroform-d)δ151.66,151.64,151.62,151.60,151.57,151.34,151.33,129.20,129.14,129.10,129.09,129.05,129 .04,128.99,128.99,128.94,128.88,115.16,115.13,115.11,115.09,115.06,113.74,113.72,113.69,113.67,113.65,73.62,73.6 1,73.59,73.57,73.55,55.69,55.67,55.65,30.40,30.34,30.25,30.18,30.09,26.93,26.90,26.88,26.85,26.82,8.78,8.73,8.67,8.62,8.56,-9.80,-9.88,-9.95,-10.03,-10.11,-10.18,-10.26,-10.34,-10.41,-10.49,-10.57,-10.64,-10.72,-10.80,-10.87.

[0092] Synthesis Example 3: Synthesis of Compound A3

[0093]

[0094] The preparation of intermediate M1 is the same as in synthesis example 1.

[0095] <Preparation of intermediate M4>

[0096] At 0 °C, intermediate M1 (10.6 mmol), DCM (10 ml), and pyridine (21.3 mmol) were added to a flame-dried flask; a solution of trifluoromethanesulfonic anhydride (12.8 mmol) in DCM (5 ml) was added dropwise; the reaction mixture was stirred at room temperature for 1.5 hours; the mixture was quenched by adding diethyl ether (15 ml) and HCl aqueous solution (10%, 5 ml); the reaction mixture was washed successively with saturated NaHCO3 aqueous solution (10 ml) and brine (10 ml); the mixture was dried with MgSO4; the solvent was evaporated under reduced pressure; the residue was purified by distillation using a high-temperature distillation apparatus (model B-585Kugelrohr) to obtain intermediate M4.

[0097] <Preparation of intermediate M6>

[0098] Catalyst Pd (1.0 mol), intermediate M4 (1.0 mmol), 7-thiocyanate-propaneboric acid (1.2 mmol), potassium carbonate (2.0 mmol), N,N-dimethylformamide (DMF, 10 ml), and water (2.5 ml) were mixed in a stainless steel reactor. The mixture was stirred at 100 °C. After the reaction was completed, the reaction mixture was extracted with diethyl ether and potassium hydroxide solution to remove the remaining boric acid. The mixture was dried with MgSO4, filtered, and the solvent in the filtrate was evaporated to obtain thiocyanate-protected intermediate M6.

[0099] <Preparation of Compound A3>

[0100] In a three-necked round-bottom flask, toluene (Tol, 25 ml) solution was added to intermediate M6 (10 mmol) and stirred until homogeneous. Then, P2S5 (10 mmol) was added, and the resulting suspension was refluxed back into the flask. After the reaction was complete, water (10 ml) was carefully added to quench the reaction mixture, and the mixture was extracted with ethyl acetate (30 ml). The organic phase was dried over NaSO4 and evaporated under reduced pressure to obtain the crude product. Compound A3 was purified by rapid chromatography (hexane-ethyl acetate) to obtain compound A3.

[0101] NMR data for compound A3:

[0102] 1 H NMR (400MHz, CDCl3 / DMSO) δ6.89–6.69(m,10H),4.27–4.17(m,10H),3.90(t,J=1.0Hz,2 H),3.86–3.73(m,22H),2.70–2.57(m,11H),2.17(t,J=6.8Hz,1H),1.96–1.80(m,15H).

[0103] 13C NMR(100MHz,Chloroform-d)δ152.98,152.96,152.94,152.93,152.91,151.65,151.64,129.03,128 .98,128.93,128.87,128.82,128.77,128.72,128.67,114.79,114.77,114.75,114.73,114.72,112. 67,112.65,112.64,112.63,112.61,68.55,68.53,68.51,68.50,68.48,55.71,55.69,55.67,32.14,32.11,32.09,32.07,32.04,30.60,30.55,30.47,30.41,30.12,23.91,23.86,23.81,23.75,23.70.

[0104] Synthesis Example 4: Synthesis of Compound A4

[0105]

[0106] <Preparation of intermediate M4> is the same as in synthesis example 3.

[0107] <Preparation of intermediate M7>

[0108] Catalyst Pd (1.0 mol), intermediate M4 (1.0 mmol), tert-butyl 7-carbamate-propaneboronic acid (1.2 mmol), potassium carbonate (2.0 mmol), DMF (10 ml), and water (2.5 ml) were mixed in a stainless steel reactor. The mixture was stirred at 100 °C. After the reaction was completed, the reaction mixture was extracted with diethyl ether and potassium hydroxide solution to remove the remaining boric acid. The mixture was dried with MgSO4, filtered, and the solvent in the filtrate was evaporated to obtain intermediate M7 protected by tert-butyloxycarbonyl (Boc).

[0109] <Preparation of Compound A4>

[0110] Intermediate M7 was dissolved in 10 ml of dry DCM to obtain a 0.1 mol / L solution. Trifluoroacetic acid (TFA, 1 mmol) was added to the above solution, and the reaction mixture was stirred slowly while maintaining the reaction temperature at 0-5 °C for 30 minutes. Then, 1 ml of ethanol was added, and H3BO3 was added dropwise to bring the pH of the reaction system close to neutral. The reaction mixture was transferred to a separatory funnel and extracted three times with anhydrous DCM to remove unreacted reagents and byproducts. The organic phase (upper layer) was collected, dried with anhydrous Na2SO4, and then evaporated to dryness to obtain the deprotected compound A4.

[0111] NMR data for compound A4:

[0112] 1 H NMR (400MHz, CDCl3 / DMSO) δ6.87(t,J=1.1Hz,1H),6.82–6.68(m,8H),6.68(t,J=1.0Hz,1H),5.07(td,J=6.2,1.2 Hz,9H),4.10–3.97(m,11H),3.90(t,J=1.0Hz,2H),3.86–3.70(m,22H),3.00–2.82(m,11H),1.88–1.72(m,11H).

[0113] 13 C NMR(100MHz,Chloroform-d)δ152.91,152.89,152.87,152.86,152.84,151.65,151.64,129.05, 129.00,128.95,128.90,128.87,128.85,128.82,128.77,128.72,128.67,114.01,114.00,113.9 9,113.98,113.96,112.16,112.14,112.13,67.95,67.93,67.91,67.89,67.87,55.69,36.82,36.80,36.78,36.75,36.73,31.66,31.63,31.60,31.57,31.53,30.50,30.44,30.36,30.30,30.12.

[0114] Synthesis Example 5: Synthesis of Compound A5

[0115]

[0116] <Preparation of intermediate M2> is the same as in synthesis example 1.

[0117] <Preparation of Compound A5>

[0118] t-BuONa (2.67 mmol) and 4-n-heptanol pyridine (2.67 mmol) were added to a CH3CN (10 mL) solution of intermediate M2 (2.8 mmol). The mixture was stirred and heated at 80 °C for 16 hours. After cooling, the solid was filtered, and the filtrate was concentrated. The residue was purified by normal-phase chromatography, eluting with a mixture of ethyl acetate and heptane (v / v, 15:85). The crude mixture was dissolved in ethyl acetate, washed with NaOH (1 mol / L), and the solvent was removed by distillation. The crystals yielded compound A5.

[0119] NMR data for compound A5:

[0120] 1 H NMR (400MHz, CDCl3 / DMSO) δ8.52(ddd,J=5.9,2.0,0.9Hz,10H),7.28–7.20(m,10H),6.75(p,J=1.0Hz,5H),6.72(dq,J=1.9,0. 9Hz,5H),3.96–3.84(m,20H),3.84–3.77(m,15H),2.61(t,J=6.4Hz,9H),1.84(p,J=6.4Hz,10H),1.62(p,J=6.6Hz,10H),1.52–

[0121] 1.39(m,11H),1.39–1.22(m,21H).

[0122] 13 C NMR(100MHz,Chloroform-d)δ152.46,151.51,151.47,149.01,127.56,127.52,123.81, 115.31,113.05,65.38,55.68,34.88,31.99,30.96,30.86,29.56,29.40,28.87,26.55.

[0123] Synthesis Example 6: Synthesis of Compound A6

[0124]

[0125] The preparation of intermediate M1 is the same as in Synthesis Example 1.

[0126] <Preparation of intermediate M5>

[0127] Intermediate M1 (10 mmol) and 1,7-dibromoheptane (80 mmol) were added to a mixed solvent of CH3CN (30 ml) and anhydrous potassium carbonate (40 mmol); the reaction mixture was refluxed and stirred in an oil bath for 10 hours; potassium carbonate was removed by suction filtration and solvent was removed under reduced pressure; the crude residue was purified by column chromatography to obtain intermediate M5.

[0128] <Preparation of Compound A6>

[0129] t-BuOLi (0.45 mmol) and 4-dimethylaminopyridine (DMAP, 0.24 mmol) were added to a 10 mL reaction tube under a nitrogen atmosphere and mixed. Then, dimethyl sulfoxide (DMSO, 1.5 mL), hexamethyldimethylformane (0.42 mmol), and intermediate M3 (0.3 mmol) were added sequentially to the reaction tube. The mixture was then stirred in an oil bath at 80 °C for 1 hour. The reaction mixture was filtered through a chromatography column to remove insoluble precipitates. The crude product was then purified by silica gel column chromatography (PE to EA volume ratio 100:1) to obtain compound A6.

[0130] NMR data for compound A6:

[0131] 1 H NMR (400MHz, CDCl3 / DMSO) δ6.78(dq,J=1.9,1.0Hz,5H),6.72(dp,J=1.8,1.0Hz,5H),3.93(dt,J=1.9,0.9Hz,11H),3.8 5(t,J=6.1Hz,10H),3.76–3.69(m,16H),1.84(q,J=6.1Hz,22H),1.55(s,35H),1.52–1.39(m,24H),1.37–1.24(m,22H).

[0132] 13 C NMR(100MHz,Chloroform-d)δ151.18,150.80,128.28,127.60,115.44,113.94,64 .93,55.59,33.97,30.37,30.33,30.28,29.62,29.26,26.66,26.27,9.15,-10.35.

[0133] Synthesis Example 7: Synthesis of Compound A7

[0134]

[0135] <Preparation of intermediate M4> is the same as in synthesis example 3.

[0136] <Preparation of intermediate M8>

[0137] Catalyst Pd (1.0 mol), intermediate M4 (1.0 mmol), 7-thiocyanate-heptylboronic acid (1.2 mmol), potassium carbonate (2.0 mmol), DMF (10 ml), and water (2.5 ml) were mixed in a stainless steel reactor. The mixture was stirred at 100 °C. After the reaction was completed, the reaction mixture was extracted with diethyl ether and potassium hydroxide solution to remove the remaining boric acid. The mixture was dried with MgSO4, filtered, and the solvent in the filtrate was evaporated to obtain thiocyanate-protected intermediate M8.

[0138] <Preparation of Compound A7>

[0139] In a three-necked round-bottom flask, toluene (Tol, 25 ml) solution was added to intermediate M8 (10 mmol) and stirred until homogeneous. Then, P2S5 (10 mmol) was added, and the resulting suspension was refluxed back into the flask. After the reaction was complete, water (10 ml) was carefully added to quench the reaction mixture, and the mixture was extracted with ethyl acetate (30 ml). The organic phase was dried over NaSO4 and evaporated under reduced pressure to obtain the crude product. Compound A7 was purified by rapid chromatography (hexane-ethyl acetate) to obtain compound A7.

[0140] NMR data for compound A7:

[0141] 1 H NMR(400MHz, CDCl3 / DMSO)δ6.88(dt,J=7.0,1.1Hz,2H),6.83–6.69(m,8H),3.94– 3.83(m,12H),3.88–3.73(m,21H),2.62–2.47(m,11H),1.90–1.78(m,10H),1.64–

[0142] 1.51(m,10H),1.56–1.37(m,26H),1.34–1.20(m,10H).

[0143] 13C NMR(100MHz,Chloroform-d)δ152.80,152.78,152.77,152.75,152.74,151.61,151.60,129.02,128.97,128.92,128.86,128.81,128 .75,128.70,115.07,115.05,115.03,115.00,114.98,113.05,113.03,113.02,113.00,112.98,66.45,66.43,66.41,66.39,66.37,55 .73,55.72,55.70,33.63,33.59,33.56,33.52,33.49,31.63,31.61,31.59,31.56,30.35,29.52,29.48,29.45,29.41,29.38,29.17,29.15,29.12,29.10,29.07,28.60,28.58,28.56,28.54,28.52,26.36,26.35,26.34,26.32,26.31,24.91,24.84,24.77,24.70,24.63.

[0144] Synthesis Example 8: Synthesis of Compound A8

[0145]

[0146] <Preparation of intermediate M4> is the same as in synthesis example 3.

[0147] <Preparation of intermediate M9>

[0148] Catalyst Pd (1.0 mol), intermediate M4 (1.0 mmol), tert-butyl 7-carbamate-heptylboronic acid (1.2 mmol), potassium carbonate (2.0 mmol), DMF (10 ml), and water (2.5 ml) were mixed in a stainless steel reactor. The mixture was stirred at 100 °C. After the reaction was completed, the reaction mixture was extracted with diethyl ether and potassium hydroxide solution to remove the remaining boric acid. The mixture was dried with MgSO4, filtered, and the solvent in the filtrate was evaporated to obtain intermediate M9 protected by tert-butyloxycarbonyl (Boc).

[0149] <Preparation of Compound A8>

[0150] Intermediate M9 was dissolved in 10 ml of dry DCM to obtain a 0.1 mol / L solution. Trifluoroacetic acid (TFA, 1 mmol) was added to the above solution, and the reaction mixture was stirred slowly while maintaining the reaction temperature at 0-5 °C for 30 minutes. Then, 1 ml of ethanol was added, and H3BO3 was added dropwise to bring the pH of the reaction system close to neutral. The reaction mixture was transferred to a separatory funnel and extracted three times with anhydrous DCM to remove unreacted reagents and byproducts. The organic phase (upper layer) was collected, dried with anhydrous Na2SO4, and then evaporated to dryness to obtain the deprotected compound A8.

[0151] NMR data for compound A8:

[0152] 1 H NMR (400MHz, CDCl3 / DMSO) δ6.86(dt,J=6.0,1.0Hz,2H),6.86–6.73(m,6H),6.74(t,J=1.0Hz,1H),6.66(t,J=1.0Hz,1H),3.97–3.83(m, 13H),3.85–3.70(m,22H),2.73–2.60(m,10H),2.03(td,J=6.2,1.2Hz,9H),1.90–1.68(m,20H),1.52–1.35(m,11H),1.40–1.24(m,20H).

[0153] 13C NMR(100MHz,Chloroform-d)δ152.80,152.78,152.77,152.75,152.74,151.61,151.60,128.90,128.87,128.84,128.82,128.79,128.77,12 8.74,128.72,128.68,128.67,114.93,114.90,114.88,114.86,114.8 4,113.00,112.98,112.97,112.95,112.93,66.45,66.43,66.41,66.3 9,66.37,55.74,55.73,55.72,41.93,41.90,41.88,41.86,41.84,33.82,33.78,33.74,33.71,33.67,31.63,31.61,31.59,31.56,30.35,29.52,29.49,29.45,29.42,29.38,29.10,29.07,29.05,29.02,28.99,27.11,27.09,27.08,27.06,27.04,26.51,26.50,26.48,26.47,26.46.

[0154] Other compounds within the scope of this application can be synthesized by selecting suitable raw materials in accordance with the ideas of Synthesis Examples 1 to 8 above, or by selecting any other suitable method and raw materials.

[0155] Example 1

[0156] (1) Using a silicon wafer as a substrate, the silicon wafer was pretreated. Specifically, the silicon wafer was cut into 2cm×2cm pieces, then placed in a piranha solution and heated at 110℃ for 3 hours. Afterward, it was ultrasonicated in ultrapure water for 15 minutes to obtain a clean silicon wafer with a silicon dioxide layer. The silicon wafer was an N-type doped silicon wafer (provided by Silicon Valley Microelectronics Co., Ltd.), containing a silicon dioxide layer and a silicon substrate, with a resistivity of 0.004 Ω·cm. Under light-shielded conditions, ultraviolet photoresist (brand name AR-P-5350) was spin-coated onto the clean silicon wafer with the silicon dioxide layer (silicon oxide wafer), and then dried. Then, the mask for the gate pattern was aligned with the silicon wafer for photolithography, and exposed for 5 seconds using an ultraviolet lithography machine. A 10nm Cr layer was first deposited on the silicon oxide wafer using vacuum evaporation deposition technology, followed by a 50nm Au layer. Finally, the wafer was soaked in acetone for approximately 4 hours to remove the photoresist, yielding a metal gate electrode-silicon oxide wafer. In this design, the Cr layer serves as the adhesion layer between the Au layer and the underlying silicon substrate, and the metal gate electrode is used to establish external gate test sites. The metal gate electrode is annular in shape, with an inner diameter of 100 μm and an outer diameter of 150 μm; the silicon oxide wafer has a thickness of 100 nm.

[0157] Under light-protected conditions, photoresist is spin-coated onto a silicon oxide wafer and exposed. A mask with a 10μm diameter circular hole is aligned with the inner circle of the gate pattern for photolithography. After development and fixing, it is dried with an air gun. Then, BOE solution is used to etch the circular holes that are not protected by the photoresist until the 100nm silicon dioxide layer is completely etched, exposing the underlying silicon to obtain a circular blind hole with a diameter of 4μm.

[0158] (2) A 10nm Cr layer is first deposited at the bottom of the blind hole using vacuum evaporation coating technology, followed by a 60nm Au layer as the source electrode. Finally, the photoresist on the substrate is removed with acetone and annealed at 327°C to make the Au layer have an atomically flat surface, thus obtaining a semi-finished device with a source electrode.

[0159] (3) Dissolve the columnar aromatic hydrocarbon compound A1 in ultra-dry ethanol solvent to prepare a solution of compound A1 with a molar concentration of 0.5 mmol / L; immerse the obtained semi-finished device in the above solution for 6 h, then wash and dry it. Then immerse it in a 0.5 mmol / L silver trifluoroacetate aqueous solution for 6 h, remove it, wash and dry it to form a self-assembled monolayer on the source electrode, and obtain a semi-finished device with a self-assembled monolayer, wherein the molar ratio of columnar aromatic hydrocarbon molecules to silver ions is 1:1, and the thickness of the self-assembled monolayer is 1.29 nm.

[0160] (4) First, monolayer graphene was grown on Cu(111) foil using chemical vapor deposition (CVD). The specific steps were as follows: a 2cm×2cm Cu(111) foil was placed in a tube furnace and treated in a hydrogen atmosphere with a hydrogen flow rate of 16ml / min. Then, graphene was grown in a mixed atmosphere of methane and hydrogen with a methane flow rate of 1.6ml / min and a hydrogen flow rate of 8ml / min until the Cu(111) foil was completely covered by monolayer graphene. Then, a photoresist polymethyl methacrylate (PMMA) was spin-coated onto the front side of a Cu(111) foil with a single layer of graphite to obtain a multilayer structure of "PMMA / graphene film / copper foil / graphene film". Next, oxygen plasma etching (oxygen plasma flow rate of 20 sccm, processing time of 120 s) was used to remove the outer graphene film in the "PMMA / graphene film / copper foil / graphene film" structure, resulting in a three-layer structure of "PMMA / graphene film / copper foil". Then, the "PMMA / graphene film / copper foil" structure was immersed in a 20% ferric chloride solution until the Cu foil was completely dissolved, yielding a "PMMA / graphene film" structure. The "PMMA / " structure was then... The graphene film structure was sequentially immersed in five hydrochloric acid solutions with decreasing concentrations of 1.00%, 0.50%, 0.10%, 0.05%, and 0.01% (by mass) for cleaning, followed by soaking in deionized water for 20 minutes. The washed PMMA / graphene film structure was then placed in isopropanol to remove water. A semi-finished device with a self-assembled monolayer was used to remove the PMMA / graphene film structure from the isopropanol solvent, allowing the solvent to evaporate naturally. This allowed the graphene film to adhere smoothly to the surface of the semi-finished device. Finally, the semi-finished device was placed in boiling acetone for 5 minutes to remove PMMA from its surface. Then, under light-protected conditions, photoresist was spin-coated onto the graphene film surface and dried. Then, photolithography was performed by aligning the blind apertures of a mask with a circular hole pattern of 80 μm in diameter. After development and fixing, the image was dried with an air gun. Plasma etching was then used to remove the graphene without photoresist protection, and finally, acetone was used to remove the photoresist. Photoresist was then spin-coated again, and a drain pattern was photolithographically formed on the graphene using ultraviolet lithography. After development and fixing, the image was dried with an air gun. A 10 nm Cr layer was first deposited on the drain pattern using vacuum evaporation deposition technology, followed by a 50 nm Au layer as the metal drain electrode, used for external drain test sites. The thickness of the drain graphene was 0.35 nm.

[0161] (5) Diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imine (DEME-TFSI) ionic liquid is dropped onto the drain as a gate, and the ionic liquid simultaneously covers the annular metal gate electrode pattern, the drain pattern and graphene.

[0162] Examples 2 to 8

[0163] Except for adjusting the types of column aromatic molecules according to Table 1, everything else is the same as in Example 1.

[0164] The preparation parameters and performance tests for each embodiment are shown in Table 1.

[0165] Table 1

[0166]

[0167] As can be seen from Examples 1-8 in Table 1, the vertical monomolecular memristor provided in this application, using columnar aromatic hydrocarbon molecules within the scope of this application, can achieve the switching control between high and low resistance values ​​by regulating the movement of silver ions within the cavity of the columnar aromatic hydrocarbon molecules through voltage regulation, thus obtaining a tunable vertical monomolecular memristor with a maximum on / off rectification ratio of 3.1 × 10⁻⁶. 4 It has a higher on / off rectification ratio than the traditional metal oxide memristor, which is 1.2 × 10⁻⁶. 2 This demonstrates that the vertical monomolecular film memristor of this application has a higher on / off rectification ratio, i.e., a highly efficient vertical monomolecular film memristor is obtained. After placing the vertical monomolecular film memristors prepared in Examples 1-8 in a room temperature, air environment for 7 days, the vertical monomolecular film memristors can still achieve switching control between high and low resistance values, and still maintain a high on / off rectification ratio. This indicates that the vertical monomolecular film memristor of this application has good stability.

[0168] As can be seen from Examples 1-8, within the scope of this application, a structurally stable, efficient, and tunable vertical monomolecular memristor can be obtained by considering the chemical bonds formed between the source and the self-assembled monomolecular film, the molar ratio of columnar aromatic molecules and silver ions, the material and thickness of the source, the material and thickness of the drain, the gate, and the thickness of the self-assembled monomolecular film.

[0169] Figure 2 The IV characteristic curves of the vertical monomolecular membrane memristor in Example 1 are shown. As the voltage increases from 0V to 1V, the vertical monomolecular membrane memristor is in a high-resistance state, during which the current is relatively small. When the voltage increases to 1V, under the influence of the electric field, silver ions move within the cavity of the columnar aromatic hydrocarbon molecules, and the vertical monomolecular membrane memristor transitions from a high-resistance state to a low-resistance state. At a voltage of 0.7V, the current I0 corresponding to the high-resistance state is 7.1 × 10⁻⁶. -8 A, the corresponding current I in the low resistance state. max 3.54×10 -5 A, calculate the on / off rectification ratio I max / I0 is 5.0 × 10 2Then, the voltage is gradually decreased from 1V to 0V. The vertical monomolecular memristor remains in a low-resistance state, and the current gradually decreases to 0A as the voltage decreases. Next, the voltage is increased from 0V to -1V. The vertical monomolecular memristor remains in a low-resistance state, and the current is relatively small during this process. When the voltage increases to -1V, under the influence of the electric field, silver ions move within the cavity of the columnar aromatic hydrocarbon molecules, and the vertical monomolecular memristor transitions from a low-resistance state to a high-resistance state, with a sharp drop in current. Then, the voltage is gradually decreased from -1V to 0V. The vertical monomolecular memristor remains in a high-resistance state, and the current gradually decreases to 0A as the voltage decreases. This demonstrates that applying the columnar aromatic hydrocarbon molecule system to a vertical monomolecular memristor allows for the control of silver ion movement within the cavity of the columnar aromatic hydrocarbon molecules by adjusting the voltage, achieving the transition between high and low resistance values, thus obtaining a tunable vertical monomolecular memristor.

[0170] Figure 3 The image shows the IV characteristic curve of the vertical monomolecular memristor from Example 1 after being placed in room temperature air for 7 days. From Figure 3 It can be seen that the vertical monomolecular membrane memristor, after being placed in room temperature air environment for 7 days, can also achieve the conversion between high resistance and low resistance, that is, the vertical monomolecular membrane memristor provided in this application has good stability.

[0171] The various embodiments in this specification are described in a related manner. The same or similar parts between the various embodiments can be referred to each other. Each embodiment focuses on describing the differences from other embodiments.

[0172] The above description is merely a preferred embodiment of this application and is not intended to limit the scope of protection of this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application are included within the scope of protection of this application.

Claims

1. A vertical monomolecular memristor, comprising a substrate, a source electrode, a self-assembled monomolecular film, a drain electrode, and a gate electrode sequentially disposed on the substrate; wherein the self-assembled monomolecular film comprises a columnar aromatic hydrocarbon molecular system, the columnar aromatic hydrocarbon molecular system being composed of columnar aromatic hydrocarbon molecules and silver ions, and the structural formula of the columnar aromatic hydrocarbon molecules is shown in Formula A: in, n is 5; R1 is selected from hydrogen or methyl; R2 is selected from the groups shown in Formulas I-IV below, where m is an integer from 1 to 10; The group R2 in the columnar aromatic hydrocarbon molecule is connected to the source electrode by a chemical bond, and the group R1 in the columnar aromatic hydrocarbon molecule is connected to the drain electrode by van der Waals forces.

2. The vertical monomolecular memristor according to claim 1, wherein, The columnar aromatic molecule is selected from compounds represented by formulas A1-A8:

3. The vertical monomolecular memristor according to claim 1, wherein, The self-assembled monolayer is obtained by the self-assembly of the columnar aromatic hydrocarbon molecular system on the source electrode; the molar ratio of the columnar aromatic hydrocarbon molecules to the silver ions is 1:0.5-1.

4. The vertical monomolecular memristor according to claim 1, wherein, The source electrode material is selected from Au, Ag, or Pt; the chemical bond is selected from covalent or coordinate bonds. R2 in the columnar aromatic molecule is selected from formula I, the chemical bond is a coordinate bond, and the coordinate bond is a coordinate bond formed between a pyridinyl group and the source electrode; or R2 in the columnar aromatic molecule is selected from formula II, the chemical bond is a covalent bond, and the covalent bond is a C-Au bond, a C-Ag bond, or a C-Pt bond; or R2 in the columnar aromatic molecule is selected from formula III, the chemical bond is a covalent bond, and the covalent bond is an S-Au bond, a S-Ag bond, or a S-Pt bond; or R2 in the columnar aromatic molecule is selected from formula IV, the chemical bond is a coordinate bond, and the coordinate bond is a coordinate bond formed between an amino group and the source electrode.

5. The vertical monomolecular memristor according to claim 1, wherein, The drain electrode is made of graphene; the gate electrode is an ionic liquid gate.

6. The vertical monomolecular memristor according to claim 1, wherein, The substrate includes a substrate bottom layer and an oxide layer. The substrate bottom layer is made of silicon, mica or sapphire, and the oxide layer is made of silicon dioxide, hafnium dioxide or aluminum oxide.

7. The vertical monomolecular memristor according to claim 1, wherein, The thickness of the self-assembled monolayer is 0.7 nm-3 nm; the thickness of the source electrode is 50 nm-90 nm; and the thickness of the drain electrode is 0.3 nm-3 nm.

8. A method for preparing a vertical monomolecular film memristor according to any one of claims 1-7, comprising the following steps: (1) A blind hole is provided on the substrate, the bottom of the blind hole being exposed above the bottom layer of the substrate; (2) The source electrode is disposed in the blind hole; (3) The columnar aromatic molecules are self-assembled on the source electrode, and the silver ions are introduced by adding silver trifluoroacetate solution to obtain the self-assembled monolayer. (4) The drain electrode is disposed on the self-assembled monolayer; (5) The gate is disposed on the drain to obtain the vertical monomolecular memristor.

Images