CN116217573A - Vertical monomolecular film field effect control switch and preparation method thereof - Google Patents

Vertical monomolecular film field effect control switch and preparation method thereof Download PDF

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CN116217573A
CN116217573A CN202310160890.1A CN202310160890A CN116217573A CN 116217573 A CN116217573 A CN 116217573A CN 202310160890 A CN202310160890 A CN 202310160890A CN 116217573 A CN116217573 A CN 116217573A
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conductive metal
monomolecular film
effect control
field effect
layer
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郭雪峰
李萌萌
周丽
句宏宇
张恩予
贾传成
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Nankai University
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

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Abstract

The application provides a vertical monomolecular film field effect control switch and a preparation method thereof, wherein the vertical monomolecular film field effect control switch adopts bistable [2] rotaxane molecules at room temperature, and under different bias actions, the bistable [2] rotaxane molecules can be switched between a low-conductivity state and a high-conductivity state, so that a device can be sensitively and rapidly switched between switch states; further, the vertical monomolecular film field effect control switch comprises a semiconductor basal layer, a conductive metal source electrode, an insulating supporting layer, a self-assembled monomolecular film, a single-layer graphene drain electrode, a conductive metal gate electrode and an ion gate, wherein the self-assembled monomolecular film is composed of the [2] rotaxane molecules; the vertical monomolecular film field effect control switch provided by the application has stronger gate electric field regulation and control capability and better stability.

Description

Vertical monomolecular film field effect control switch and preparation method thereof
Technical Field
The application relates to the technical field of molecular switching devices, in particular to a vertical monomolecular film field effect control switch and a preparation method thereof.
Background
Molecular field effect devices at the molecular scale are capable of operating in the quantum tunneling state and are the most likely electronic components in future integrated circuits. The operation of molecular field effect control switches is typically regulated by a voltage applied to the gate. In general, a solid back gate or an electrochemical gate is placed on one side of a molecular junction, and the gate voltage is adjusted to regulate and control the molecular energy level position, so as to change the relative position of the molecular energy level and the fermi level of an electrode, thereby achieving the purpose of regulating and controlling the electric conductance of the molecular junction. However, the gate electric field intensity of the molecular switch based on the solid gate electric field regulation molecular level is weak, the regulation efficiency is low, and the stability is poor. The gate and the dielectric layer are in direct contact with molecules, so that the molecular heterojunction is unstable, the intensity of gate regulation is reduced, and the stability of the device is reduced.
Disclosure of Invention
The invention aims to provide a vertical monomolecular film field effect control switch and a preparation method thereof, so as to obtain the vertical monomolecular film field effect control switch with strong gate regulation and control capability and good stability at room temperature. The specific technical scheme is as follows:
the first aspect of the present application provides a vertical monomolecular film field effect control switch comprising [2 ] ]A rotaxane molecule; said [2]]The rotaxane molecule consists of cyclic ions and linear moleculesThe method comprises the steps of carrying out a first treatment on the surface of the The cyclic ion is CBPQT 4+ The structure is as follows:
Figure BDA0004094093640000011
the structural formula of the linear molecule is shown as formula A:
X 1 —Q 1 —R 1 —Q 2 —R 2 —Q 3 —X 2
formula A;
wherein X is 1 Selected from the group consisting of
Figure BDA0004094093640000021
Q 1 Is->
Figure BDA0004094093640000022
R 1 Selected from->
Figure BDA0004094093640000023
Q 2 Selected from->
Figure BDA0004094093640000024
/>
Figure BDA0004094093640000025
R 2 Is->
Figure BDA0004094093640000026
Q 3 Is->
Figure BDA0004094093640000027
X 2 Is->
Figure BDA0004094093640000028
A second aspect of the present application provides a method for preparing a vertical monomolecular film field effect control switch provided in the first aspect of the present application, which includes the following steps:
1) Preparing a semiconductor substrate layer and an insulating support layer, wherein the insulating support layer is an upper layer, and the semiconductor substrate layer is a lower layer;
2) Preparing a conductive metal gate electrode on the upper surface of the insulating support layer;
3) Preparing a round hole in the insulating supporting layer to expose a bottom semiconductor substrate, and preparing a conductive metal source electrode on the upper surface of the bottom semiconductor substrate;
4) Self-assembling the [2] rotaxane molecule and the conductive metal source end electrode to obtain a self-assembled monomolecular film; the self-assembled monomolecular film is composed of the [2] rotaxane molecules;
5) Completely covering the single-layer graphene on the top of the round hole to obtain a single-layer graphene drain electrode;
6) Preparing a conductive metal drain electrode at the outer side of the single-layer graphene drain electrode relative to the other side of the conductive metal gate electrode;
7) And covering an ion grid, wherein the ion grid completely covers the single-layer graphene drain electrode and the conductive metal drain electrode, and partially covers the conductive metal grid electrode.
The application provides a vertical monomolecular film field effect control switch and a preparation method thereof, wherein the vertical monomolecular film field effect control switch adopts bistable [2] rotaxane molecules at room temperature, and under different bias actions, the bistable [2] rotaxane molecules can be switched between a low-conductivity state and a high-conductivity state, so that a device can be sensitively and rapidly switched between switch states; further, the vertical monomolecular film field effect control switch comprises a semiconductor basal layer, a conductive metal source electrode, an insulating supporting layer, a self-assembled monomolecular film, a single-layer graphene drain electrode, a conductive metal gate electrode and an ion gate, wherein the self-assembled monomolecular film is composed of the [2] rotaxane molecules; the vertical monomolecular film field effect control switch provided by the application has stronger gate electric field regulation and control capability and better stability.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following description will briefly introduce the drawings that are required to be used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other embodiments may also be obtained according to these drawings to those skilled in the art.
FIG. 1 is a three-dimensional block diagram of a vertical monolayer field effect control switch of the present application;
FIG. 2 is a top view of a vertical monolayer field effect control switch structure of the present application;
the reference numerals are: 1. the semiconductor substrate layer, the conductive metal source electrode, the insulating support layer, the self-assembled monomolecular film, the single-layer graphene drain electrode, the conductive metal gate electrode and the ion gate electrode are respectively arranged on the semiconductor substrate layer, the conductive metal source electrode, the insulating support layer, the self-assembled monomolecular film, the single-layer graphene drain electrode, the conductive metal gate electrode and the ion gate electrode;
FIG. 3 is a schematic diagram showing the structural transition between the oxidation state and the reduction state of the [2] rotaxane molecule A1;
FIG. 4 is a graph showing the current versus source drain voltage for the vertical monolayer field effect control switch of example 1 at a gate voltage of-0.5V;
FIG. 5 is a graph showing the current versus source drain voltage for the vertical monolayer field effect control switch of example 1 at a gate voltage of 0V;
FIG. 6 is a graph showing the current versus source drain voltage for the vertical monolayer field effect control switch of example 1 at a gate voltage of 0.5V;
FIG. 7 is a graph showing the current versus source drain voltage for the vertical monolayer field effect control switch of example 2 at a gate voltage of-0.5V;
FIG. 8 is a graph showing the current versus source drain voltage for the vertical monolayer field effect control switch of example 2 at a gate voltage of 0V;
FIG. 9 is a graph showing the current versus source drain voltage for the vertical monolayer field effect control switch of example 2 at a gate voltage of 0.5V;
FIG. 10 is a graph showing the variation of current with source-drain voltage for the vertical monolayer field effect control switch of example 3 at a gate voltage of-0.5V;
FIG. 11 is a graph showing the current versus source drain voltage for the vertical monolayer field effect control switch of example 3 at a gate voltage of 0V;
FIG. 12 is a graph showing the current versus source drain voltage for the vertical monolayer field effect control switch of example 3 at a gate voltage of 0.5V.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. Based on the embodiments herein, a person of ordinary skill in the art would be able to obtain all other embodiments based on the disclosure herein, which are within the scope of the disclosure herein.
The first aspect of the present application provides a vertical monomolecular film field effect control switch comprising [2 ]]A rotaxane molecule; said [2 ] ]The rotaxane molecule consists of cyclic ions and linear molecules; the cyclic ion is CBPQT 4+ (Cyclobis (parallel-p-phenyl) with the structure:
Figure BDA0004094093640000041
the structural formula of the linear molecule is shown as formula A:
X 1 —Q 1 —R 1 —Q 2 —R 2 —Q 3 —X 2
formula A;
wherein X is 1 Selected from the group consisting of
Figure BDA0004094093640000042
Q 1 Is->
Figure BDA0004094093640000043
R 1 Selected from->
Figure BDA0004094093640000044
Q 2 Selected from->
Figure BDA0004094093640000045
Figure BDA0004094093640000051
R 2 Is->
Figure BDA0004094093640000052
Q 3 Is->
Figure BDA0004094093640000053
X 2 Is->
Figure BDA0004094093640000054
In the application, the [2] rotaxane molecule is formed by the cyclic ion and the linear molecule through a supermolecular acting force, the [2] rotaxane molecule has bistable property at room temperature, and the stable switching of the on-off state of the device can be realized under voltage control.
In some embodiments of the first aspect of the present application, the [2] rotaxane molecule is selected from any of A1 to A3:
Figure BDA0004094093640000061
in some embodiments of the first aspect of the present application, the vertical monomolecular film field effect control switch comprises a semiconductor substrate layer, a conductive metal source electrode, an insulating support layer, a self-assembled monomolecular film (SAMs), a single layer graphene drain electrode, a conductive metal gate electrode, and an ion gate; the self-assembled monolayer is composed of the [2] rotaxane molecule.
In the application, both ends of the [2] rotaxane molecule are hydrophobic groups, one of the ends contains trimethylsilane or trimethylsilylacetylene, and an Au-C, ag-C or Pt-C chemical bond is formed between the trimethylsilane or trimethylsilylacetylene removed and the conductive metal source electrode, so that the self-assembled monomolecular film and the conductive metal source electrode can be stably connected; the other end is a multi-benzene ring structure of pyrene or anthracene, so that stronger van der Waals acting force can be formed between the self-assembled monomolecular film and the single-layer graphene drain electrode.
The vertical monomolecular film field effect control switch provided by the application adopts the [2] rotaxane molecules with bistable states and the ultra-flat conductive metal source end electrode, and the stability of the connection between the [2] rotaxane molecules and the conductive metal source end electrode and the protection effect of the insulating support layer and the single-layer graphene drain end electrode on the self-assembled monomolecular film are utilized, so that the switching stability of the device at room temperature can be improved; the single-layer graphene is adopted as the drain electrode, so that the transmission distance of charges can be reduced, the self-assembled monomolecular film and the graphene are connected through stronger van der Waals interaction, the transmission speed of charges can be improved, the running speed and the stability of the device are further improved, and the device is sensitively and rapidly switched between switch states; the hydrogel type ion grid electrode is adopted, so that the thickness of the grid electrode can be shortened, and the control capability of the grid electrode on a device switch and the stability of the grid electrode are improved.
In some embodiments of the first aspect of the present application, the self-assembled monolayer has a thickness of 3-9nm.
In the application, the thickness of the self-assembled monomolecular film is the length of the [2] rotaxane molecule; the sum of the thickness of the self-assembled monolayer and the thickness of the conductive metal source electrode is equal to the thickness of the insulating support layer.
In some embodiments of the first aspect of the present application, the semiconductor material of the semiconductor base layer is selected from Si or gallium arsenide (GaAs); the insulating material of the insulating supporting layer is selected from SiO 2 Silicon nitride (Si) 3 N 4 ) Or gallium sulfide (GaS); the thickness of the insulating supporting layer is 80-120nm.
In some embodiments of the first aspect of the present application, the metal materials of the conductive metal source electrode, the conductive metal drain electrode, and the conductive metal gate electrode are respectively selected from Cr/Au, cr/Ag, or Cr/Pt; the thickness of the metal material is (10-20 nm)/(50-100 nm) respectively.
In this application, the conductive metal source electrode, the conductive metal drain electrode, and the conductive metal gate electrode may be obtained by evaporation: firstly, evaporating a layer of Cr with the thickness of 5-20nm, and then evaporating a layer of Au, ag or Pt with the thickness of 50-100 nm.
In some embodiments of the first aspect of the present application, the thickness of the conductive metal source electrode is 91-97nm.
In some embodiments of the first aspect of the present application, the conductive metal source electrode is circular and has a diameter of 1-2 μm; the single-layer graphene drain electrode is round, and the diameter is 60-150 mu m; the conductive metal drain electrode is semi-circular, the outer diameter is 100-180 mu m, and the inner diameter is 60-120 mu m; the conductive metal gate electrode is semicircular, the outer diameter is 220-280 mu m, and the inner diameter is 180-240 mu m;
The single-layer graphene drain electrode completely covers the conductive metal source electrode; the ion grid completely covers the single-layer graphene drain electrode and the conductive metal drain electrode, and partially covers the conductive metal grid electrode.
In the application, the outer diameter of the conductive metal drain electrode is larger than the diameter of the single-layer graphene drain electrode, and the inner diameter of the conductive metal drain electrode is smaller than the diameter of the single-layer graphene drain electrode.
In the application, the single-layer graphene drain electrode can be obtained by Chemical Vapor Deposition (CVD) -dry transfer or chemical vapor deposition-wet transfer, and then the single-layer graphene drain electrode with the diameter of 60-150 mu m is prepared by photoetching and oxygen plasma etching methods.
In some embodiments of the first aspect of the present application, a center of the single-layer graphene drain electrode is located directly above a center of the conductive metal source electrode.
In some embodiments of the first aspect of the present application, the ion grid is a hydrogel material storing LiF, liCl or NaCl salt ions, the salt ion concentration being 1×10 -2 -1mol/L; the polymer monomer of the hydrogel material is selected from acrylic acid, acrylamide, vinyl alcohol, sodium styrene sulfonate or methacryloyloxyethyl trimethyl ammonium chloride; the polymerization degree of the polymer is not particularly limited as long as the object of the present application can be achieved, and the polymer is a polymer having a high polymerization degree The degree of polymerization of the polymer may be several thousands to several millions, and the degree of polymerization of the polymer is, illustratively, 5×10 3 -1×10 6 。
According to the vertical monomolecular film field effect control switch, the hydrogel type ion grid is adopted, so that the grid regulation and control capability can be improved, meanwhile, the defect of high fluidity of the traditional ion liquid grid is avoided, and the field effect control switch can stably operate at room temperature; the gate electric field provided by the ion gate is vertically applied to the self-assembled monomolecular film through a single-layer graphene structure, so that the direct contact between a metal drain electrode and a [2] rotaxane molecule is avoided, the distance between the [2] rotaxane molecule and the gate is controlled at the electron tunneling scale, and the stability of the device and the gate regulation and control efficiency are greatly improved.
A second aspect of the present application provides a method for preparing a vertical monomolecular film field effect control switch provided in the first aspect of the present application, which includes the following steps:
1) Preparing a semiconductor substrate layer and an insulating support layer, wherein the insulating support layer is an upper layer, and the semiconductor substrate layer is a lower layer;
2) Preparing a conductive metal gate electrode on the upper surface of the insulating support layer;
3) Preparing a round hole in the insulating supporting layer to expose a bottom semiconductor substrate, and preparing a conductive metal source electrode on the upper surface of the bottom semiconductor substrate;
4) Self-assembling the [2] rotaxane molecule and the conductive metal source end electrode to obtain a self-assembled monomolecular film; the self-assembled monomolecular film is composed of the [2] rotaxane molecules;
5) Completely covering the single-layer graphene on the top of the round hole to obtain a single-layer graphene drain electrode;
6) Preparing a conductive metal drain electrode at the outer side of the single-layer graphene drain electrode relative to the other side of the conductive metal gate electrode;
7) And covering an ion grid, wherein the ion grid completely covers the single-layer graphene drain electrode and the conductive metal drain electrode, and partially covers the conductive metal grid electrode.
The vertical monomolecular film field effect control switch is a cross-plane vertical field effect control switch, the three-dimensional structure of the vertical monomolecular film field effect control switch is shown in figure 1, the top view of the vertical monomolecular film field effect control switch is shown in figure 2, and the other side of the vertical monomolecular film field effect control switch opposite to the position of the conductive metal gate electrode is provided with two conductive metal drain electrodes opposite to each other with round isolating holes; the application adopts a bistable [2] rotaxane molecule at room temperature, the bistable [2] rotaxane molecule can be switched between a low-conductivity state and a high-conductivity state under different bias actions, and as an example, the [2] rotaxane molecule A1 disclosed by the application has different charge transmission capacities, namely different molecular conductivities, in an oxidation state (high-conductivity state, representing ON, a right side structure of fig. 3) and a reduction state (low-conductivity state, representing OFF, a left side structure of fig. 3) in a structure conversion schematic diagram shown in fig. 3, wherein the [2] rotaxane molecule is subjected to oxidation or reduction reactions under different voltage actions corresponding to different molecular configurations.
In the present application, the "high conductivity state" and the "low conductivity state" refer to two conductivity states of the vertical monomolecular film field effect control switch under specific conditions, wherein the conductivity refers to a ratio of a current to a bias voltage corresponding to the current; the conductance of the high conductance state is greater than the conductance of the low conductance state.
The vertical monomolecular film field effect control switch prepared by the preparation method has stronger gate electric field regulation and control capability and better stability.
In some embodiments of the second aspect of the present application, the self-assembly comprises:
dissolving the [2] rotaxane molecule in a solvent to prepare a molecular solution;
dissolving tetrabutylammonium fluoride (TBFA) in the same solvent as the molecular solution to prepare a deprotected solution;
mixing the molecular solution and the deprotection solution to obtain a mixed solution;
immersing the semi-finished device obtained in the step 3) into the mixed solution for 10-14h, taking out, washing and drying;
wherein the solvent is acetonitrile or acetone; in the molecular solution, the [2]]The concentration of rotaxane molecules was 0.5X10 -3 -2×10 -3 mol/L; the concentration of tetrabutylammonium fluoride in the deprotected solution is 1X 10 -3 -3×10 -3 mol/L。
In the application, trimethylsilane or trimethylsilyl acetylene at the tail end of the [2] rotaxane molecule is removed by utilizing TBFA, so that the [2] rotaxane molecule is connected with a metal atom through a carbon atom at the tail end to form a bond, thereby forming a self-assembled monomolecular film on a conductive metal source end electrode, and the other tail end group of the monomolecular film is connected with a single-layer graphene drain end electrode covered on the molecular film through van der Waals acting force.
In some embodiments of the second aspect of the present application, the conductive metal drain electrode and the conductive metal gate electrode are prepared by photolithography-evaporation of metal electrodes, respectively;
the conductive metal source electrode is prepared by magnetron sputtering coating, atomic Layer Deposition (ALD) or vacuum evaporation coating, and is annealed in a gas of 200-300 ℃ for 1-2h, wherein the gas is argon or hydrogen;
the round holes in the insulating support layer are prepared in a photoetching-etching mode;
the single-layer graphene drain electrode is obtained by means of chemical vapor deposition-dry transfer or chemical vapor deposition-wet transfer.
In the application, the diameter of the round hole in the insulating supporting layer is 1-2 mu m.
In the application, the preparation method of the conductive metal source electrode is adopted to obtain the ultra-flat conductive metal source electrode, and the ultra-flat conductive metal source electrode has an atomically flat surface, so that the stability of a device can be further improved.
In the present application, the single-layer graphene drain electrode may be obtained by chemical vapor deposition-wet transfer, and is exemplified by: (1) Firstly, epitaxially growing single-layer graphene on a Cu (111) foil by using a chemical vapor deposition method; (2) Spin-coating polymethyl methacrylate (PMMA) glue on one side of graphene, drying to form a PMMA-graphene-copper foil-graphene structure, and then etching the structure by oxygen plasma to remove single-layer graphene on one side to form the PMMA-graphene-copper foil structure; (3) Sticking an adhesive tape on the edge of the PMMA-graphene-copper foil so as to facilitate subsequent transfer; (4) Placing the structure into ferric chloride solution, enabling the Cu foil to be in contact with the ferric chloride solution and carrying out chemical reaction until Cu is completely removed by reaction, forming a PMMA-graphene structure, and fishing out the PMMA-graphene structure by using a clean silicon wafer; (5) Sequentially placing the PMMA-graphene structure into three hydrochloric acid solutions with gradient descending concentration for cleaning and soaking, fishing out the PMMA-graphene structure by using a clean silicon wafer, and finally cleaning and soaking the PMMA-graphene structure in deionized water for twenty minutes and fishing out the PMMA-graphene structure by using the clean silicon wafer; (6) Putting the PMMA-graphene structure into isopropanol solvent to remove water, then fishing out the PMMA-graphene structure by using a semi-finished product device assembled with the [2] rotaxane monomolecular film, attaching a single-layer graphene to the surface of the semi-finished product device, airing, and removing an adhesive tape at the edge; (7) And then putting the semi-finished device attached with the PMMA-graphene structure into boiled acetone, taking out after half an hour, and removing PMMA glue.
In the present application, the single-layer graphene drain electrode may be obtained by chemical vapor deposition-dry transfer, and is exemplified by: (1) Firstly, epitaxially growing single-layer graphene on a Cu (111) foil by using a chemical vapor deposition method; (2) Attaching a thermal stripping adhesive tape (polydimethylsiloxane, PDMS) on one side of graphene to form a PDMS-graphene-copper foil-graphene structure, and then etching the structure by oxygen plasma to remove one side of single-layer graphene to form the PDMS-graphene-copper foil structure; (3) Placing the structure into ferric chloride solution, enabling the Cu foil to be in contact with the ferric chloride solution and performing chemical reaction until Cu is completely removed by reaction, and forming a PDMS-graphene structure; (4) Sequentially placing the PDMS-graphene structure into three hydrochloric acid solutions with gradient descending concentration for cleaning and soaking, fishing out the PDMS-graphene structure by using a clean silicon wafer, and finally cleaning and soaking the PDMS-graphene structure in deionized water for twenty minutes and fishing out the PDMS-graphene structure by using the clean silicon wafer; (5) Putting the PDMS-graphene structure into isopropanol solvent to remove water, then fishing out the semi-finished product device assembled with the [2] rotaxane monomolecular film, attaching single-layer graphene to the surface of the semi-finished product device, and airing; (6) And heating the semi-finished device attached with the PDMS-graphene structure to 80-120 ℃ to enable the PDMS to lose viscosity and separate from the graphene.
Hereinafter, the present application will be specifically described based on examples, but the present application is not limited to the following examples. The experimental materials and methods used in the examples below are conventional materials and methods unless otherwise specified.
The electrical test is under vacuum condition<1×10 -4 Pa). Test instrument: agilent 4155C semiconductor tester, ST-500-probe station (Janis Research Company), comprehensive physical Property test System (PPMS). The test temperature is precisely regulated and controlled by liquid nitrogen, liquid helium and a heating platform.
And (3) electrical testing: and at any temperature of 248-303K temperature range, when the fixed gate voltages are-0.5V, 0V and 0.5V respectively, the source-drain voltage is applied to scan from-2V to +2V and then scan to-2V, and the current-voltage characteristic curve of the vertical monomolecular film field effect control switch along with the voltage change is measured.
Example 1 vertical Mono-molecular film field Effect control switch based on Compound A1
(1) Preparation of compound A1:
Figure BDA0004094093640000111
/>
Figure BDA0004094093640000121
p-trimethylsilylphenol 1 (1.96 g,10 mmol), 2- (2-chloroethoxy) ethanol 2 (1.31 g,11 mol), potassium carbonate (K) 2 CO 3 A solution of 2.76g,20 mol) and potassium iodide (KI, 20 mg) in N, N-dimethylformamide (DMF, 100 mL) was stirred at 100deg.C for 16h. After cooling to room temperature, DMF was removed in vacuo and the residue was subjected to column chromatography (silica column chromatography, eluent: ethyl acetate/hexane, 1/1) to give compound 3 (2.30 g, yield 81%) as a colorless oil. 1 H NMR(500MHz,Chloroform-d)δ7.45–7.39(m,2H),6.98–6.92(m,2H),4.13(t,J＝5.0Hz,2H),3.75(t,J＝5.0Hz,2H),3.68–3.61(m,2H),3.60–3.55(m,2H),2.92(t,J＝6.3Hz,1H),0.25(s,8H). 13 C NMR(125MHz,Chloroform-d)δ161.76,133.10,116.63,114.79,104.72,94.90,72.62,69.88,68.07,61.89 Mass Spectrometry (electron bombardment Source) (MS (EI)) M/z (%) 284 (37) [ M+1)] + .
Compound 3 (1.56 g,5.5 mmol), p-toluenesulfonyl chloride (TsCl, 1.14mg,6.0 mmol), 4-dimethylaminopyridine (DMAP, 10 mg) and triethylamine (Et) 3 N,1.4mL,10 mmol) was placed in dry dichloromethane (CH 2 Cl 2 50 mL) was stirred at room temperature for 16h. After silica (7.0 g) was added, the mixture was concentrated and purified by short-path column chromatography (silica column chromatography, eluent: ethyl acetate/hexane, 1:4) to give tosylate 4 as a colorless oil. Tosylate 4 (1.31 g,3.0 mmol), 1-acetoxy-5-hydroxynaphthalene 5 (708 mg, 3.5 mmol), potassium carbonate (8238 g,6.0 mmol), lithium bromide (15 mg) and 18-crown-6 (18C 6, 10 mg) were heated under reflux in acetonitrile (MeCN, 50 mL) for 16h. After cooling to room temperature, the reaction mixture was filtered and the solid was washed with acetonitrile (100 mL). The filtrate was concentrated, and then crude compound 6 was dissolved in methanol (100 mL). Potassium hydroxide (KOH, 560 mg,10 mmol) was added and the reaction mixture was stirred at room temperature for 4h. Column chromatography (silica column chromatography, eluent: ethyl acetate/hexane, 1:2) of the crude product gave compound 7 (941 mg, total yield 72%) as an off-white solid. 1 H NMR(500MHz,Chloroform-d)δ8.97(s,1H),8.04–7.99(m,1H),7.97–7.91(m,1H),7.45–7.39(m,2H),7.29–7.19(m,2H),6.99–6.92(m,3H),6.91–6.86(m,1H),4.20(t,J＝4.9Hz,2H),4.12(t,J＝5.0Hz,2H),3.70(dt,J＝8.1,5.0Hz,4H),0.25(s,8H). 13 C NMR(125MHz,Chloroform-d)δ161.76,153.98,153.28,133.10,126.44,125.74,125.63,124.72,119.03,116.63,116.35,114.79,110.27,108.72,104.72,94.90,70.44,70.09,68.87,68.14.MS(EI)m/z(％)436.3(53)[M] + .
A solution of iodide 9 (2- (2- (2-iodoethoxy) ethoxy) tetrahydro-2H-pyran, 9.09g,30.3 mmol) in tetrahydrofuran (THF, 200 mL) was added dropwise to compound 8 ((Z) - [2,2' -bis (1, 3-dithioethylene)]In a solution of 4,4' -diyldimethanol, 2.00g,7.89 mmol) and NaH (1.39 g,60.6 mmol) in THF (900 mL) was heated at reflux for 1h. The mixture was then stirred by reflux for 48h. Crude compound 10 was obtained as brown, dissolved in methanol (MeOH)/Dichloromethane (DCM) (1:1, 200 mL)And (3) oil. Hydrochloric acid solution (mass fraction: 10%,0.5 mL) was then added thereto, and the mixture was stirred at room temperature for 2 hours. By column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 The crude product was purified with MeOH, 100/3) to give compound 11 (2.08 g, 60% yield) as orange oil. 1 H NMR(500MHz,Chloroform-d)δ6.45(t,J＝1.0Hz,2H),4.28(d,J＝1.1Hz,4H),3.72(t,J＝4.8Hz,4H),3.68–3.59(m,9H),3.57(t,J＝4.5Hz,4H). 13 C NMR (125 MHz, chloroform-d) delta 131.86,120.03,120.00,71.73,70.85,69.79,61.89.MS (fast atom bombardment Source (FAB)) M/z (%) 440 (40) [ M] + .
At 0deg.C, tsCl (634 mg,3.3 mmol) in CH 2 Cl 2 (10 mL) solution was added dropwise compound 11 (1.63 g,3.7 mmol), et 3 N (2.57 mL,18.5 mmol) and DMAP (15 mg) and then stirred at room temperature for 16h. By column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 Ethanol (EtOH), 100/3) to afford compound 12 (989 mg, 45% yield) as a yellow oil. 1 H NMR(500MHz,Chloroform-d)δ7.74–7.68(m,2H),7.40(dq,J＝8.3,0.8Hz,2H),6.45(d,J＝1.0Hz,2H),4.28(d,J＝1.0Hz,4H),4.20(t,J＝6.0Hz,2H),3.75–3.68(m,6H),3.68–3.54(m,9H),2.41(d,J＝0.9Hz,3H). 13 CNMR(125MHz,Chloroform-d)δ142.69,132.99,131.90,131.86,129.78,127.91,120.10,120.04,120.03,120.00,71.73,70.88,70.85,69.80,69.62,68.87,68.74,61.89,21.51.MS(FAB)m/z(％)594.05(43)[M] + .
Compound 12 (990 mg, 1.67 mmol), 1-hydroxypyrene 13 (1.17 g, 5.00 mmol), potassium carbonate (1.38 g,10 mmol), lithium bromide (10 mg) and 18-crown-6 (10 mg) in dry acetonitrile (50 mL) were heated under reflux for 16h. By column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 EtOH,100: 3) Purification gave compound 14 (1.07 g, 95% yield) as a yellow solid. Compound 14 (428 mg,0.95 mmol), tsCl (362 mg,1.9 mmol), DMAP (10 mg) and Et 3 A solution of N (1.1 mL,7.6 mmol) was dissolved in anhydrous dichloromethane (50 mL) and stirred at room temperature for 16h. By column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 EtOH,100: 3) The crude residue was purified to give compound 15 (691 mg)Yield 88%) as yellow solid. 1 H NMR(500MHz,Chloroform-d)δ7.80–7.74(m,1H),7.74–7.67(m,2H),7.66–7.55(m,2H),7.40(dq,J＝8.5,0.8Hz,2H),7.01(d,J＝8.4Hz,1H),6.78(dq,J＝9.0,0.8Hz,1H),6.45(d,J＝1.0Hz,2H),6.17(dt,J＝9.0,4.9Hz,1H),5.88(tt,J＝5.1,1.0Hz,1H),4.28(d,J＝1.0Hz,4H),4.24–4.15(m,4H),3.92(ddt,J＝18.0,5.1,0.9Hz,1H),3.75(t,J＝4.9Hz,2H),3.75–3.62(m,7H),3.67–3.57(m,4H),3.43(dp,J＝4.9,1.0Hz,2H),2.41(d,J＝0.9Hz,3H). 13 C NMR(125MHz,Chloroform-d)δ151.00,142.69,137.19,132.99,131.90,131.86,130.25,130.00,129.94,129.78,129.08,127.91,126.59,126.26,125.21,124.91,124.14,123.71,121.20,120.10,120.04,120.03,120.00,113.10,70.88,70.85,70.37,69.63,69.61,68.87,68.74,68.73,32.84,25.66,21.51.MS(FAB)m/z(％)810.24(35)[M] + .
A solution of compound 7 (1.308 mg,0.3 mmol), tosylate 15 (247.8 mg,0.3 mol), potassium carbonate (82.9 mg,0.6 mol), lithium bromide (10 mg) and 18-crown-6 (10 mg) in acetonitrile (50 mL) was heated under reflux for 16h. Column chromatography (silica column chromatography, eluent: ethyl acetate/hexane, 1:1) of the crude product gave compound 16 (222 mg, yield 68%) as a yellow solid. 1 H NMR(500MHz,Chloroform-d)δ7.95(dt,J＝7.9,0.8Hz,2H),7.80–7.73(m,1H),7.66–7.55(m,2H),7.46–7.38(m,2H),7.21(t,J＝7.9Hz,2H),7.01(d,J＝8.4Hz,1H),6.98–6.91(m,4H),6.78(dq,J＝9.0,0.8Hz,1H),6.45(t,J＝1.0Hz,2H),6.18(dt,J＝9.0,4.9Hz,1H),5.90(tt,J＝5.1,1.0Hz,1H),4.28(d,J＝1.0Hz,4H),4.25–4.09(m,9H),3.92(ddt,J＝18.0,5.1,0.9Hz,1H),3.75(t,J＝4.9Hz,2H),3.75–3.61(m,12H),3.60(t,J＝4.8Hz,4H),3.40(dp,J＝4.9,0.9Hz,1H),3.14(dp,J＝4.9,1.0Hz,1H),0.25(s,7H). 13 C NMR(125MHz,Chloroform-d)δ161.76,155.06,155.04,151.00,135.90,133.10,131.90,131.86,130.29,130.15,129.75,129.08,127.08,126.91,126.88,126.59,126.28,125.53,125.42,124.25,124.14,121.08,120.10,120.04,120.03,120.00,119.20,119.19,116.63,114.79,113.10,109.06,108.99,104.72,94.90,70.88,70.85,70.44,70.37,70.36,70.09,69.62,69.61,68.92,68.88,68.73,68.14,34.78,25.77.MS(FAB)m/z(％)1074(33)[M] + .
Compound 16 (109 mg,0.1 mmol), hexafluorophosphoric acid compound 17.2PF 6 (1, 1"- (1, 4-phenylbis (methylene)) bis ([ 4,4' -bipyridine) ]1-ium)). Dihexafluorophosphate, 332mg,0.3 mmol) and 1, 4-bis (bromomethyl) benzene 18 (124 mg,0.3 mmol) in anhydrous DMF (11 mL) were stirred at room temperature for 6 days. The reaction mixture was directly subjected to column chromatography (silica column chromatography) purification, wherein unreacted compound 16 was purified by acetone (Me 2 CO) recovery, eluting with acetone/ammonium hexafluorophosphate (NH) 4 PF 6 )(1.0g NH 4 PF 6 ，100mL Me 2 CO), collecting the mixture containing [2 ]]Rotaxane 19.4PF 6 Green stripes of (c). After removal of the solvent, water (50 mL) was added and the resulting precipitate was collected by filtration to give [2 ]]Rotaxane 19.4PF 6 (161 mg, yield 72%) as green solid, compound A1. 1 H NMR(500MHz,Chloroform-d)δ9.12–9.07(m,8H),8.71–8.66(m,8H),7.95(dt,J＝7.9,0.8Hz,2H),7.80–7.73(m,1H),7.66–7.55(m,2H),7.46–7.40(m,2H),7.39(s,7H),7.21(t,J＝7.9Hz,2H),7.01(d,J＝8.4Hz,1H),6.98–6.91(m,4H),6.78(dq,J＝9.0,0.8Hz,1H),6.45(t,J＝1.0Hz,2H),6.18(dt,J＝9.0,4.9Hz,1H),6.10(d,J＝0.9Hz,8H),5.90(tt,J＝5.1,1.0Hz,1H),4.28(d,J＝1.0Hz,4H),4.25–4.09(m,9H),3.92(ddt,J＝18.0,5.1,0.9Hz,1H),3.75(t,J＝4.9Hz,2H),3.75–3.61(m,12H),3.60(t,J＝4.8Hz,4H),3.40(dp,J＝4.9,0.9Hz,1H),3.14(dp,J＝4.9,1.0Hz,1H),0.25(s,7H). 13 C NMR(125MHz,Chloroform-d)δ161.76,155.06,155.04,151.00,147.67,146.53,135.90,134.75,133.10,131.90,131.86,130.29,130.15,129.75,129.08,128.08,127.78,127.08,126.91,126.88,126.59,126.28,125.53,125.42,124.25,124.14,121.08,120.10,120.04,120.03,120.00,119.20,119.19,116.63,114.79,113.10,109.06,108.99,104.72,94.90,70.88,70.85,70.44,70.37,70.36,70.09,69.62,69.61,68.92,68.88,68.73,68.14,64.09,34.78,25.77.MS(FAB)m/z(％)2227(45)[M] + .
(2) Preparation of vertical monomolecular film field effect control switch
Taking SiO with a wavelength of 100nm 2 Thickness of clean silicon wafer Si/SiO 2 Wherein the Si layer is a semiconductor substrate layer, siO 2 The layer is an insulating supporting layer;
at the SiO 2 The upper surface of the insulating supporting layer is provided with a conductive metal gate electrode, which comprises the following steps: under the light-shielding condition, cleaning silicon slice SiO 2 Homogenizing and drying the upper surface of the layer, then using a mask plate with a grid electrode shape to carry out local exposure, flushing for 10s by using a developing solution, fixing for 10s by using deionized water, and drying; evaporating Cr with the thickness of 10nm and Au with the thickness of 90nm on the position of the exposure pattern in sequence to serve as a conductive metal gate electrode, and then soaking the conductive metal gate electrode in acetone solution and washing out photoresist; wherein, the conductive metal gate electrode is in a semicircular shape, has an outer diameter of 240 mu m and an inner diameter of 200 mu m, and externally guides the gate electrode test site;
At the SiO 2 A round hole with the diameter of 1.5 mu m is prepared in the insulating supporting layer so as to expose a bottom Si substrate, and a conductive metal source electrode is prepared on the upper surface of the bottom Si substrate, specifically: under the condition of light shielding, under the condition of SiO 2 Homogenizing and drying the upper surface of the layer, then carrying out local exposure by using a mask plate with the shape of a source end electrode, and then developing, fixing and drying; then using buffer oxide etching solution (49% HF aqueous solution: 40% NH) 4 F aqueous solution = 1:6 (volume ratio)) etching of SiO at the exposed pattern position 2 After 5 minutes, taking out and flushing with deionized water to expose the Si substrate at the lower layer of the silicon wafer, thus obtaining the SiO with round holes 2 An insulating support layer; then plating Cr with the thickness of 10nm and Au with the thickness of 84nm on the upper surface of the Si substrate at the bottom of the round hole in a vacuum magnetron sputtering coating mode to serve as a flat conductive metal source electrode, soaking and washing photoresist with acetone solution, and annealing for 1.5 hours at the temperature of 250 ℃; wherein, the shape of the conductive metal source electrode is round, and the diameter is 1.5 mu m;
will [2 ]]The rotaxane molecule A1 and the conductive metal source electrode are subjected to chemical self-assembly to obtain a self-assembled monomolecular film, which is specifically: compound A1 was dissolved in acetonitrile to give A1 concentration of 1X 10 -3 A molecular solution of mol/L; TBFA was dissolved in acetonitrile to give a TBFA concentration of 2X 10 -3 A mol/L deprotection solution; mixing the molecular solution and the deprotection solution to obtain a mixed solution; immersing the semi-finished device obtained in the previous step into the saidTaking out the mixture after 12 hours, washing with acetonitrile and drying; at this time, the conductive metal source electrode is assembled with [2] via Au-C bond]A rotaxane monomolecular film; the thickness of the self-assembled monolayer is about 6nm;
the top of the round hole comprising the self-assembled monomolecular film is completely covered with single-layer graphene, and the method specifically comprises the following steps: placing Cu (111) foil in a tube furnace, and epitaxially growing single-layer graphene on the front and back sides of the copper foil by using a chemical vapor deposition method; spin-coating PMMA glue on graphene on one side, drying to form a PMMA-graphene-copper foil-graphene structure, and removing single-layer graphene without PMMA glue on the other side of the structure by oxygen plasma etching to form the PMMA-graphene-copper foil structure; then, sticking an adhesive tape on the PMMA edge of the PMMA-graphene-copper foil, so that the subsequent transfer is facilitated; then placing the structure into ferric chloride solution, enabling the copper foil to be in contact with the ferric chloride solution and carrying out chemical reaction until copper is completely removed, forming a PMMA-graphene structure, and fishing out the PMMA-graphene structure by using a clean silicon wafer; sequentially placing the PMMA-graphene structure into three hydrochloric acid solutions with concentration gradient decreasing (the mass fractions are 1%,0.1% and 0.01%) for cleaning and soaking, taking out the clean silicon wafer, cleaning and soaking in deionized water for twenty minutes, and taking out the clean silicon wafer; putting the PMMA-graphene structure into isopropanol solvent to remove water, then fishing out the PMMA-graphene structure by using a semi-finished product device assembled with the [2] rotaxane monomolecular film, attaching a monolayer graphene to the surface of the semi-finished product device, completely covering the top of a round hole of the self-assembled monomolecular film, airing, and removing an adhesive tape at the edge; finally, putting the semi-finished device attached with the PMMA-graphene structure into boiled acetone, taking out after half an hour, and removing PMMA glue;
Etching single-layer graphene as a drain electrode: under the condition of avoiding light, uniformly coating and drying the single-layer graphene in the last step, then carrying out local exposure by using a mask plate with the shape complementary with that of a graphene drain electrode, and then developing, fixing and drying; then, etching graphene around the circular graphene drain electrode by using oxygen plasma; then, the photoresist on the graphene drain electrode is washed away by acetone, so that a single-layer graphene drain electrode is obtained; wherein the shape of the single-layer graphene drain electrode is circular, and the diameter is 110 mu m;
and preparing a conductive metal drain electrode at the periphery of the single-layer graphene drain electrode at the other side opposite to the position of the conductive metal gate electrode, wherein the preparation method specifically comprises the following steps: under the condition of avoiding light, the structural sizing and drying of the single-layer graphene drain electrode are obtained in the last step, then the mask plate with the shape of the conductive metal drain electrode is used for carrying out local exposure, and then the single-layer graphene drain electrode is developed, fixed and dried; evaporating Cr with the thickness of 10nm and Au with the thickness of 90nm on the position of the exposure pattern in sequence to serve as conductive metal drain electrodes, and then soaking the conductive metal drain electrodes in acetone solution and washing out photoresist; the conductive metal drain electrode is in the shape of two semicircular rings with opposite round isolating holes, the conductive metal drain electrode is completely contacted with the periphery of the single-layer graphene drain electrode, the outer diameter of the conductive metal drain electrode is 120 mu m, the inner diameter of the conductive metal drain electrode is 90 mu m, and the conductive metal drain electrodes of the two semicircular rings respectively externally guide drain electrode test sites;
And covering an ion grid, wherein the ion grid completely covers the single-layer graphene drain electrode and the conductive metal drain electrode, and partially covers the conductive metal grid electrode, and the ion grid is a polyacrylamide hydrogel material with the concentration of 0.5mol/L LiF salt ions.
When the vertical monomolecular film field effect control switch is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the gate voltages are respectively-0.5V, 0V and 0.5V, the characteristic curves of the current changing along with the source-drain voltage are respectively shown in the figures 4, 5 and 6, and according to the figures 4-6, the source-drain current is increased and the molecular conductivity is improved in the process of gradually increasing the source-drain voltage from-2V to +2V; in the process that the source-drain voltage is gradually reduced from +2V to-2V, the source-drain current is reduced, and the molecular conductivity is reduced; the source-drain current increases when the gate voltage is ±0.5v with respect to the gate voltage of 0V. The temperature dependence was tested using a comprehensive testing system and found to be consistent throughout the range 248-303K. The result shows that the obtained vertical monomolecular film field effect control switch has strong regulation and control capability on molecular conductivity, has strong gate regulation and control capability, and can exist stably in an air environment.
Example 2 vertical Mono-molecular film field Effect control switch based on Compound A2
(1) Preparation of compound A2:
Figure BDA0004094093640000181
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Figure BDA0004094093640000191
a solution of iodide 2 (9.09 g,30.3 mmol) in tetrahydrofuran (THF, 200 mL) was added dropwise to a solution of compound 1 (2.00 g,7.89 mmol) and NaH (1.39 g,60.6 mmol) in THF (900 mL) under Ar and heated at reflux for 1h. The mixture was then stirred by reflux for 48h. Crude compound 3 was obtained as a brown oil dissolved in methanol (MeOH)/Dichloromethane (DCM) (1:1, 200 mL). Hydrochloric acid solution (mass fraction: 10%,0.5 mL) was then added thereto, and the mixture was stirred at room temperature for 2 hours. By column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 The crude product was purified with MeOH, 100/3) to give Compound 4 (2.08 g, 60% yield) as orange oil. 1 H NMR(500MHz,Chloroform-d)δ6.45(t,J＝1.0Hz,2H),4.28(d,J＝1.1Hz,4H),3.72(t,J＝4.8Hz,4H),3.68–3.59(m,9H),3.57(t,J＝4.5Hz,4H). 13 C NMR(125MHz,Chloroform-d)δ131.86,120.03,120.00,71.73,70.85,69.79,61.89.MS(FAB)m/z(％)440(40)[M] + .
At 0deg.C, tsCl (634 mg,3.3 mmol) in CH 2 Cl 2 (10 mL) solution was added dropwise 4 (1.63 g,3.7 mmol), et 3 N (2.57 mL,18.5 mmol) and DMAP (15 mg) and then stirred at room temperature for 16h. Column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 Ethanol (EtOH), 100/3) to give compound 5 (989 mg, 45% yield) as a yellow oil. 1 H NMR(500MHz,Chloroform-d)δ7.74–7.68(m,2H),7.40(dq,J＝8.3,0.8Hz,2H),6.45(d,J＝1.0Hz,2H),4.28(d,J＝1.0Hz,4H),4.20(t,J＝6.0Hz,2H),3.75–3.68(m,6H),3.68–3.54(m,9H),2.41(d,J＝0.9Hz,3H). 13 C NMR(125MHz,Chloroform-d)δ142.69,132.99,131.90,131.86,129.78,127.91,120.10,120.04,120.03,120.00,71.73,70.88,70.85,69.80,69.62,68.87,68.74,61.89,21.51.MS(FAB)m/z(％)594.05(43)[M] + .
5 (990 mg, 1.67 mmol), 1-hydroxypyrene 6 (1.17 g, 5.00 mmol), potassium carbonate (1.38 g,10 mmol), lithium bromide (10 mg) and 18-crown-6 (10 mg) in dry acetonitrile (50 mL) were heated under reflux for 16h. By column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 EtOH,100: 3) Purification gave compound 7 (1.07 g, 95% yield) as a yellow solid. Compound 7 (618 mg,0.95 mmol), tsCl (362 mg,1.9 mmol), DMAP (10 mg) and Et 3 A solution of N (1.1 mL,7.6 mmol) was dissolved in anhydrous dichloromethane (50 mL) and stirred at room temperature for 16h. By column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 EtOH,100: 3) The crude residue was purified to give compound 8 (691 mg, yield 88%) as a yellow solid. 1 H NMR(500MHz,Chloroform-d)δ7.80–7.74(m,1H),7.74–7.67(m,2H),7.66–7.55(m,2H),7.40(dq,J＝8.5,0.8Hz,2H),7.01(d,J＝8.4Hz,1H),6.78(dq,J＝9.0,0.8Hz,1H),6.45(d,J＝1.0Hz,2H),6.17(dt,J＝9.0,4.9Hz,1H),5.88(tt,J＝5.1,1.0Hz,1H),4.28(d,J＝1.0Hz,4H),4.24–4.15(m,4H),3.92(ddt,J＝18.0,5.1,0.9Hz,1H),3.75(t,J＝4.9Hz,2H),3.75–3.62(m,7H),3.67–3.57(m,4H),3.43(dp,J＝4.9,1.0Hz,2H),2.41(d,J＝0.9Hz,3H). 13 C NMR(125MHz,Chloroform-d)δ151.00,142.69,137.19,132.99,131.90,131.86,130.25,130.00,129.94,129.78,129.08,127.91,126.59,126.26,125.21,124.91,124.14,123.71,121.20,120.10,120.04,120.03,120.00,113.10,70.88,70.85,70.37,69.63,69.61,68.87,68.74,68.73,32.84,25.66,21.51.MS(FAB)m/z(％)810.24(35)[M] + .
P-trimethylsilylphenol 9 (1.96 g,10 mmol), 2- (2-chloroethoxy) ethanol 10 (1.31 g,11 mol), potassium carbonate (K) 2 CO 3 A solution of 2.76g,20 mol) and potassium iodide (KI, 20 mg) in N, N-dimethylformamide (DMF, 100 mL) was stirred at 100deg.C for 16h. After cooling to room temperature, DMF was removed in vacuo and the residue was subjected to column chromatography (silica column chromatography, eluent: ethyl acetate/hexane, 1/1) to give compound 11 (2.30 g, 81%),as a colourless oil. 1 H NMR(500MHz,Chloroform-d)δ7.45–7.39(m,2H),6.98–6.92(m,2H),4.13(t,J＝5.0Hz,2H),3.75(t,J＝5.0Hz,2H),3.68–3.61(m,2H),3.60–3.55(m,2H),2.92(t,J＝6.3Hz,1H),0.25(s,8H). 13 C NMR(125MHz,Chloroform-d)δ161.76,133.10,116.63,114.79,104.72,94.90,72.62,69.88,68.07,61.89.MS(EI)m/z(％)284(37)[M+1] + .
Compound 11 (1.56 g,5.5 mmol), p-toluenesulfonyl chloride (TsCl, 1.14mg,6.0 mmol), 4-dimethylaminopyridine (DMAP, 10 mg) and triethylamine (Et) 3 N,1.4mL,10 mmol) was placed in dry dichloromethane (CH 2 Cl 2 50 mL) was stirred at room temperature for 16h. After silica (7.0 g) was added, the mixture was concentrated and purified by short-path column chromatography (silica column chromatography, eluent: ethyl acetate/hexane, 1:4) to give tosylate 12 as a colorless oil. Toluene sulfonate 12 (1.31 g,3.0 mmol), (1S) -5- (2- (2-bromoethoxy) ethoxy) decahydronaphthalen-1-ol 13 (1.12 g, 3.5 mmol), potassium carbonate (8238 g,6.0 mmol), lithium bromide (15 mg) and 18-crown-6 (18C 6, 10 mg) were heated under reflux in acetonitrile (MeCN, 50 mL) for 16h. By column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 EtOH,100: 3) Purification gave compound 14 (1.27 g, 72% overall yield) as an off-white solid. 1 H NMR(500MHz,Chloroform-d)δ7.95(dt,J＝7.9,0.8Hz,2H),7.45–7.39(m,2H),7.21(t,J＝7.9Hz,2H),6.98–6.92(m,4H),4.20(td,J＝4.9,1.3Hz,4H),4.12(t,J＝5.0Hz,2H),3.86(t,J＝3.4Hz,2H),3.77(t,J＝5.0Hz,2H),3.70(dt,J＝8.1,5.0Hz,4H),3.52(t,J＝3.4Hz,2H),0.25(s,7H). 13 C NMR(125MHz,Chloroform-d)δ161.76,155.06,155.04,133.10,126.91,126.88,126.28,119.20,119.19,116.63,114.79,109.06,108.99,104.72,94.90,70.44,70.09,69.94,69.55,68.93,68.87,68.14,29.95.MS(FAB)m/z(％)586(46)[M] + .
A mixture of compound 14 (1.17 g,2.0 mmol), potassium carbonate (0.42 g,3.0 mmol) lithium bromide (7 mg), 18-crown-6 (18C 6,5 mg) and compound 15 (0.74 g,3.0 mmol) was placed in MeCN (20 mL) and heated at reflux for 16 hours. Obtaining a yellow oil, subjecting to column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 MeOH,99: 1) Purification gave compound 16 (1.18 g, 77% yield) as a white solid. 1 H NMR(500MHz,Chloroform-d)δ7.95(dt,J＝7.9,0.8Hz,2H),7.69–7.63(m,2H),7.63–7.55(m,4H),7.45–7.39(m,2H),7.21(t,J＝7.9Hz,2H),7.02–6.92(m,6H),4.20(t,J＝4.9Hz,4H),4.13(t,J＝5.0Hz,4H),3.71(dt,J＝8.1,5.0Hz,9H),0.25(s,7H). 13 C NMR(125MHz,Chloroform-d)δ161.77,159.79,155.07,155.05,139.78,133.28,133.11,131.95,128.48,128.28,126.84,126.81,126.28,121.75,119.20,119.19,116.36,115.22,114.79,109.06,109.00,104.50,94.90,70.45,70.44,70.10,70.09,68.92,68.87,68.19,68.14.MS(FAB)m/z(％)766(33)[M+1] + .
A solution of Grignard reagent 18 (3 mL,3 mmol) prepared from compound 17 was added to a solution of compound 16 (800 mg,0.8 mmol) and tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 80 mg) in anhydrous THF (10 mL) and heated at reflux for 16h. After cooling to room temperature, the solvent was evaporated to give crude compound 19 as a yellow oil. Then dissolved in methanol/dichloromethane (1:1, 50 mL), hydrochloric acid solution (mass fraction 10%,0.5 mL) was added to the mixture, and stirred at room temperature for another 16h. The crude residue was purified by column chromatography (silica column chromatography, eluent: ethyl acetate/hexane, 1:2) to give compound 20 (0.45 g, yield 71%) as a white solid. 1 H NMR(500MHz,Chloroform-d)δ7.95(dt,J＝7.9,0.8Hz,2H),7.65–7.57(m,6H),7.52–7.46(m,2H),7.45–7.39(m,2H),7.21(t,J＝7.9Hz,2H),7.02–6.92(m,7H),6.89–6.83(m,2H),4.20(t,J＝4.9Hz,4H),4.13(t,J＝5.0Hz,4H),3.71(dt,J＝8.1,5.0Hz,9H),0.25(s,8H). 13 C NMR(125MHz,Chloroform-d)δ161.76,159.78,158.00,155.06,155.04,140.86,140.68,133.33,133.10,131.45,128.48,128.39,127.99,127.96,127.92,126.91,126.88,126.28,119.20,119.19,116.63,115.85,115.22,114.79,109.06,108.99,104.72,94.90,70.45,70.44,70.10,70.09,68.92,68.87,68.19,68.14.MS(FAB)m/z(％)786(20)[M] + .
A solution of compound 20 (551 mg, 0.70 mmol), compound 8 (578 mg, 0.70 mmol), potassium carbonate (484 mg, 3.5 mol), lithium bromide (5 mg) and 18-crown-6 (5 mg) in anhydrous MeCN (20 mL) was heated under reflux for 16h. Crude productThe resultant was purified by column chromatography (silica column chromatography, eluent: ethyl acetate/hexane, 1:2) to give compound 21 (474 mg, yield 47%) as a yellow solid. 1 H NMR(500MHz,Chloroform-d)δ8.24–8.18(m,1H),8.12–8.03(m,2H),8.04(s,2H),8.01–7.85(m,5H),7.65–7.57(m,7H),7.45–7.39(m,2H),7.21(t,J＝7.9Hz,2H),7.16(d,J＝8.4Hz,1H),7.02–6.92(m,8H),6.45(t,J＝1.0Hz,2H),4.28(d,J＝1.0Hz,4H),4.22(dt,J＝16.3,5.0Hz,6H),4.13(t,J＝5.0Hz,6H),3.79–3.63(m,18H),3.60(t,J＝4.8Hz,4H),0.25(s,7H). 13 C NMR(125MHz,Chloroform-d)δ161.76,159.79,159.78,155.06,155.04,155.02,140.87,140.86,133.34,133.33,133.10,132.29,132.00,131.90,131.86,128.56,128.52,128.48,127.99,127.96,127.92,127.75,127.38,127.37,127.25,127.09,126.91,126.88,126.35,126.33,126.28,125.93,125.87,125.85,124.10,123.13,120.10,120.04,120.03,120.00,119.20,119.19,116.63,115.32,115.27,115.22,114.79,113.42,109.06,108.99,104.72,94.90,70.88,70.85,70.45,70.44,70.36,70.10,70.09,69.87,69.62,69.61,68.97,68.93,68.87,68.25,68.14,68.08.MS(FAB)m/z(％)1424(34)[M] + .
Containing Compound 21 (447 mg,0.31 mmol), compound 22.2PF 6 A solution of (640 mg,0.92 mmol) and 1, 4-bis (bromomethyl) benzene 23 (242 mg,0.92 mmol) in anhydrous DMF (30 mL) was stirred at room temperature for 10 days. The reaction mixture was directly subjected to column chromatography (silica) purification, and the recovered compound 21 was purified by acetone (Me 2 CO) elution, then changing the eluent into Me 2 CO/NH 4 PF 6 (1.0g NH 4 PF 6 ，100mL Me 2 CO), collecting the compound 24.4PF 6 Green stripes of (c). After most of the solvent was removed under vacuum, water (50 mL) was added to the residue, and the precipitate was collected by filtration and purified with diethyl ether (Et 2 O,30 mL), and vacuum drying to obtain 24.4PF 6 (312 mg, 39% yield) as a green powder, compound A2. 1 H NMR(500MHz,Chloroform-d)δ9.12–9.07(m,8H),8.71–8.66(m,8H),8.24–8.18(m,1H),8.12–8.03(m,2H),8.04(s,2H),8.01–7.85(m,5H),7.65–7.57(m,7H),7.45–7.40(m,2H),7.39(s,7H),7.21(t,J＝7.9Hz,2H),7.16(d,J＝8.4Hz,1H),7.02–6.92(m,8H),6.10(d,J＝0.9Hz,8H),6.45(t,J＝1.0Hz,2H),4.28(d,J＝1.0Hz,4H),4.22(dt,J＝16.3,5.0Hz,6H),4.13(t,J＝5.0Hz,6H),3.79–3.63(m,18H),3.60(t,J＝4.8Hz,4H),0.25(s,7H). 13 C NMR(125MHz,Chloroform-d)δ161.76,159.79,159.78,155.06,155.04,155.02,140.87,140.86,147.67,146.53,134.75,133.34,133.33,133.10,132.29,132.00,131.90,131.86,128.56,128.52,128.48,128.08,127.99,127.96,127.92,127.78,127.75,127.38,127.37,127.25,127.09,126.91,126.88,126.35,126.33,126.28,125.93,125.87,125.85,124.10,123.13,120.10,120.04,120.03,120.00,119.20,119.19,116.63,115.32,115.27,115.22,114.79,113.42,109.06,108.99,104.72,94.90,70.88,70.85,70.45,70.44,70.36,70.10,70.09,69.87,69.62,69.61,68.97,68.93,68.87,68.25,68.14,68.08,64.09.MS(FAB)m/z(％)2560(26)[M] + .
(2) Preparation of vertical monomolecular film field effect control switch
The procedure of example 1 was repeated except that the compound A2 was used in place of the compound A1.
When the vertical monomolecular film field effect control switch is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the gate voltages are respectively-0.5V, 0V and 0.5V, the characteristic curves of the current changing along with the source-drain voltage are respectively shown in the figures 7, 8 and 9, and according to the figures 7-9, the source-drain current is increased and the molecular conductivity is improved in the process of gradually increasing the source-drain voltage from-2V to +2V; in the process that the source-drain voltage is gradually reduced from +2V to-2V, the source-drain current is reduced, and the molecular conductivity is reduced; the source-drain current increases when the gate voltage is ±0.5v with respect to the gate voltage of 0V. The temperature dependence was tested using a comprehensive testing system and found to be consistent throughout the range 248-303K. The result shows that the obtained vertical monomolecular film field effect control switch has strong regulation and control capability on molecular conductivity, has strong gate regulation and control capability, and can exist stably in an air environment.
Example 3 vertical Mono-molecular film field Effect control switch based on Compound A3
(1) Preparation of compound A3:
Figure BDA0004094093640000241
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Figure BDA0004094093640000251
compound 1 (5 h,5'h-2,2' -bis [1, 3)]Dithio [4,5-c]Azole alkylene, 0.80g,2.83 mmol) was dissolved in anhydrous DMF (30 mL), cooled to 0deg.C, and vented (N 2 10 min) and then iodide 2 (2.50 g,8.33 mmol) and then NaH (0.80 g of a 60% suspension in mineral oil, 20.0 mmol) were added to the solution. The reaction mixture was stirred at 0deg.C for 3h, then diluted with dichloromethane (500 mL), washed with saturated sodium chloride solution (1500 mL), and dried (magnesium sulfate). Removing solvent to obtain brown oil, purifying by column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 Methanol (MeOH) 19: 1). The broad yellow band was collected and concentrated to give compound 3 (1.19 g, 67% yield) as a yellow oil. 1 H NMR(500MHz,Chloroform-d)δ6.45(s,3H),4.72–4.66(m,2H),4.03(t,J＝3.7Hz,4H),3.81–3.58(m,17H),1.69–1.55(m,12H). 13 C NMR(125MHz,Chloroform-d)δ122.08,119.00,116.44,99.71,69.97,69.26,66.13,63.51,47.96,30.55,25.38,19.88.MS(EI):m/z(％):626(24)[M + ].
A solution of compound 3 (1.14 g,1.82 mmol) in Tetrahydrofuran (THF)/ethanol (EtOH) (50 mL, 1:1) was degassed (N) before the addition of p-toluene sulfonic acid (TsOH, 10 mg) 2 10 min). The yellow solution was stirred at room temperature for 20h, then diluted with dichloromethane (100 mL). The combined organic phases were washed with saturated aqueous sodium bicarbonate (200 mL), water (300 mL) and dried (magnesium sulfate). Concentrated in vacuo to a yellow powder, which was then subjected to column chromatography (silica column chromatography, eluent: CH 2 Cl 2 MeOH 24: 1) And (5) purifying. The yellow-green band was collected and the solvent was evaporated to give compound 4 (0.56 g, 67% yield) as a yellow powder. 4-toluenesulfonyl chloride (TsCl, 0.57g,2.99 mmol) dissolved in dry dichloromethane (30 mL) was added dropwise to compound 4 (1.30 g, 2.83 mmol), et at a rate of 20-30min 3 N (2 mL, 1.5g, 14 mmol) and 4-dimethylaminopyridine (DMAP, 10 mg) in dry dichloromethane (90 mL). The reaction mixture was stirred for 20h (0 ℃ C. To room temperature) then alumina (10 g) was added and the solvent was removed. The green powder obtained was directly subjected to column chromatography (silica), disulfonate (0.90 g, yield 41%) was eluted with methylene chloride, and then the eluent was changed to CH 2 Cl 2 Methanol (99:1), huang Sedai containing the desired monosulfonate was collected, and compound 5 (0.38 g, 22% yield) was concentrated as a yellow solid. 1 H NMR(500MHz,Chloroform-d)δ7.74–7.68(m,2H),7.40(dq,J＝8.3,0.9Hz,2H),6.45(s,4H),4.20(t,J＝6.0Hz,2H),4.03(t,J＝3.7Hz,4H),3.74–3.62(m,8H),3.58(t,J＝4.6Hz,2H),2.41(d,J＝1.0Hz,3H). 13 C NMR (125 MHz, color-d) delta 142.69,132.99,129.78,127.91,122.18,122.13,122.08,119.09,119.00,116.53,116.49,116.44,71.78,70.27,70.02,68.91,68.73,61.50,48.03,47.98,21.51.MS (matrix assisted laser desorption ionization-time of flight (MALDI-TOF)): M/z (%) 612 (100) [ M + ].
By CH 2 Cl 2 MeOH (23:2) eluted with starting material 4 (0.45 g, 34% yield). Heating at 75℃with a mixture of monosulphonate 5 (0.37 g,0.60 mmol), 1-hydroxypyrene 6 (0.42 g,1.80 mmol), potassium carbonate (0.50 g,3.6 mmol), lithium bromide (10 mg, cat) and [18 ]]A solution of crown-6 (10 mg) in anhydrous MeCN (50 mL) for 20h. After cooling to room temperature, the reaction mixture was filtered and the residue was thoroughly washed with MeCN (20 mL). The organic filtrate was concentrated in vacuo and purified by column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 /Me 2 CO 97: 3) The yellow residue was purified. The yellow band was collected and the solvent was evaporated to give compound 7 (0.28 g, 70% yield) as a yellow foam. Containing Compound 7 (0.28 g,0.41 mmol), tsCl (0.16 g,0.82 mmol), et 3 A solution of N (0.5 mL,0.35g,3.3 mmol) and DMAP (10 mg, cat) was added to anhydrous dichloromethane (150 mL) and stirred at room temperature for 20h. Adding aluminum oxide (10 g), removing solvent, and subjecting to column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 /Me 2 CO 99: 1) The residue was purified. The yellow band was collected and the solvent was evaporated to give compound 8 (0.27 g, 81% yield) as a yellow foam. 1 H NMR(500MHz,Chloroform-d)δ7.99(d,J＝8.4Hz,1H),7.88–7.82(m,1H),7.76–7.68(m,3H),7.43–7.34(m,4H),7.32(d,J＝8.6Hz,1H),6.93(d,J＝8.6Hz,1H),6.45(s,4H),4.24–4.17(m,4H),4.03(td,J＝3.7,1.5Hz,4H),3.76–3.68(m,4H),3.65(t,J＝3.7Hz,4H),3.18–3.05(m,4H),2.41(d,J＝0.9Hz,3H). 13 C NMR (. Delta.153.81, 142.69,136.73,132.99,132.37,132.36,130.29,129.78,129.37,127.91,126.50,126.29,125.55,125.16,124.93,123.90,123.11,122.18,122.13,122.08,119.09,119.00,116.53,116.49,116.44,112.99,70.04,70.02,69.24,68.91,68.88,68.73,48.01,47.63,30.79,30.47,21.51.MS (Fourier transform-matrix assisted laser Desorption ionization) (FT-MALDI)): M/z (%) 824 (100) [ M.M. + ].
Will contain potassium carbonate (0.34 g,2.4 mmol), lithium bromide (10 mg), [18 ]]A solution of crown ether-6 (10 mg) in anhydrous MeCN (50 mL) was added tosylate 8 (0.50 g,0.60 mmol) and compound 9 (5- (2- ((tetrahydro-2H-pyran-2-yl) oxy) ethoxy) ethoxynaphthalene-1-ol, 0.26g,0.79 mmol) and heated at reflux for 20H. After cooling to room temperature, the reaction mixture was filtered and the residue was washed with MeCN (100 mL). Concentrating the organic phase filtrate in vacuo, and subjecting to column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 EtOH 97: 3) The yellow oily residue was purified. The yellow band was collected and the solvent was evaporated to give compound 10 (0.36 g, 60% yield) as a yellow foam. 1 H NMR(500MHz,Chloroform-d)δ7.98–7.91(m,2H),7.25–7.11(m,4H),7.04(dt,J＝9.0,1.2Hz,1H),6.98–6.92(m,2H),6.92–6.77(m,4H),6.73(ddt,J＝9.0,7.9,1.0Hz,1H),6.56(dt,J＝7.9,1.1Hz,1H),6.45(s,4H),4.69(td,J＝2.5,2.1,1.0Hz,1H),4.51(dqd,J＝7.4,1.8,0.9Hz,1H),4.42(dqd,J＝7.5,1.8,0.9Hz,1H),4.25–4.16(m,4H),4.19–4.08(m,2H),4.03(td,J＝3.7,1.2Hz,4H),3.81–3.54(m,17H),1.69–1.55(m,6H). 13 C NMR(125MHz,Chloroform-d)δ155.43,155.06,155.04,134.24,133.43,131.69,128.32,127.67,127.62,127.58,127.53,127.00,126.91,126.88,126.41,126.28,125.11,122.18,122.13,122.08,119.20,119.19,119.09,119.00,116.53,116.49,116.44,116.07,109.45,109.06,108.99,99.71,70.37,70.04,70.02,69.63,69.24,69.07,68.93,68.88,68.59,66.14,63.51,47.67,47.63,47.43,43.09,30.55,25.38,19.88.MS(FT-MALDI):m/z(％):998(100)[M + ].
A solution of compound 10 (0.32 g,0.32 mmol) in THF/EtOH (40 mL, 1:1) was degassed (N) before adding TsOH (10 mg) 2 10 min). The yellow solution was stirred at room temperature for 16h, then diluted with dichloromethane (50 mL). The combined organic phases were washed with saturated aqueous sodium bicarbonate (50 mL) and water (50 mL) and dried (magnesium sulfate). Concentrating in vacuo to yellow oil, and subjecting to column chromatography (silica column chromatography, eluent: CH) 2 Cl 2 Ethyl acetate 1: 1). The yellow band was collected and the solvent was evaporated to give compound 11 (0.16 g, 56% yield) as a yellow foam. Containing Compound 11 (0.16 g,0.17 mmol), tsCl (0.068 g,0.35 mmol), et 3 A solution of N (0.2 mL,0.14g,1.4 mmol) and DMAP (10 mg) in anhydrous dichloromethane (50 mL) was stirred at room temperature for 20h, then the solvent was removed and the yellow solid was purified by column chromatography (silica column chromatography, eluent: dichloromethane/ethyl acetate 19:1). The yellow bands were collected and the solvent was evaporated to give compound 12 (0.18 g, 98% yield) as a yellow foam. 1 H NMR(500MHz,Chloroform-d)δ7.98–7.92(m,2H),7.74–7.68(m,2H),7.40(dq,J＝8.3,0.8Hz,2H),7.21(t,J＝7.9Hz,2H),7.18–7.12(m,2H),7.04(dt,J＝9.0,1.2Hz,1H),6.97–6.92(m,2H),6.92–6.77(m,4H),6.73(ddt,J＝9.0,7.9,1.0Hz,1H),6.56(dt,J＝7.9,1.1Hz,1H),6.45(s,4H),4.51(dqd,J＝7.4,1.8,0.9Hz,1H),4.42(dqd,J＝7.5,1.8,0.9Hz,1H),4.26–4.17(m,6H),4.20–4.09(m,2H),4.03(td,J＝3.7,1.2Hz,4H),3.79–3.62(m,13H),2.41(d,J＝0.9Hz,3H). 13 C NMR(125MHz,Chloroform-d)δ155.43,155.06,155.04,142.69,134.24,133.43,132.99,131.69,129.78,128.32,127.91,127.67,127.62,127.58,127.53,127.00,126.91,126.88,126.41,126.28,125.11,122.18,122.13,122.08,119.20,119.19,119.09,119.00,116.53,116.49,116.44,116.07,109.45,109.06,108.99,70.38,70.04,70.02,69.24,69.07,68.93,68.88,68.87,68.76,68.59,47.67,47.63,47.43,43.09,21.51.MS(FT-MALDI):m/z(％):1068(100)[M + ].
Containing Compound 12 (0.17 g,0.16 mmol), p-trimethylsilylphenol 13 (0.05g,0.18 0.24mmol), potassium carbonate (0.09 g,0.64 mmol), lithium bromide (10 mg) and A solution of 18-crown-6 (18C 6, 10 mg) in acetonitrile (MeCN, 50 mL) was heated under reflux for 20h. After cooling to room temperature, the reaction mixture was filtered and the solid was washed with acetonitrile (100 mL). The combined organic extracts were dried (magnesium sulfate), concentrated in vacuo to a yellow oil, and purified by column chromatography (deactivated silica column chromatography, eluent: dichloromethane/ethyl acetate 3:2). The yellow band was collected and the solvent was evaporated to give compound 14 (0.12 g, 68% yield) as a yellow foam. 1 H NMR(500MHz,Chloroform-d)δ7.95(dt,J＝7.9,0.8Hz,2H),7.21(t,J＝7.9Hz,2H),7.18–7.11(m,2H),7.04(dt,J＝9.0,1.2Hz,1H),6.98–6.92(m,2H),6.92–6.77(m,4H),6.73(ddt,J＝9.0,7.9,1.0Hz,1H),6.56(dt,J＝7.9,1.1Hz,1H),6.45(s,4H),4.51(dqd,J＝7.4,1.8,0.9Hz,1H),4.46–4.38(m,1H),4.21(td,J＝5.0,3.1Hz,4H),4.19–4.08(m,2H),4.03(td,J＝3.7,0.8Hz,4H),3.83(p,J＝4.7Hz,1H),3.78–3.55(m,14H),2.59(p,J＝6.3Hz,1H),1.94–1.59(m,9H),0.16(s,7H). 13 C NMR(125MHz,Chloroform-d)δ155.43,155.06,155.04,134.24,133.43,131.70,128.32,127.67,127.62,127.58,127.53,127.00,126.91,126.88,126.41,126.28,125.11,122.18,122.13,122.08,119.20,119.19,119.09,119.00,116.53,116.49,116.44,116.07,109.45,109.06,108.99,106.99,90.80,70.99,70.37,70.04,70.02,69.24,69.07,68.93,68.88,68.59,67.80,47.67,47.63,47.43,43.09,30.11,29.52,27.69.MS(MALDI-TOF):m/z(％):1092(100)[M + ].
Compound 14 (1.09 g,0.10 mmol), compound 15.2PF 6 A solution of (0.22 g,0.31 mmol) and 1, 4-bis (bromomethyl) benzene 16 (0.082 g,0.31 mmol) in anhydrous DMF (8 mL) was transferred to a polytetrafluoroethylene tube and subjected to a pressure of 10kbar at room temperature for 3 days. The green brown solution was directly subjected to column chromatography (silica) with Me 2 CO elutes unreacted Compound 14 and then changes the eluent to Me 2 CO/NH 4 PF 6 (1.0g NH 4 PF 6 ，100mL Me 2 CO)(Ion exchange with NH 4 PF 6 ) The green-brown band was collected. Most of the solvent was in vacuo (T<30 ℃) was removed and then water (100 mL) was added. The resulting precipitate was collected by filtration, washed with water (40 mL) and diethyl ether (Et 2 O,60 mL) and vacuum on phosphorus pentoxideDrying to obtain the compound 17.4PF 6 (0.10 g, 47% yield) as a brown solid, compound A3. 1 H NMR(500MHz,Chloroform-d)δ9.12–9.07(m,8H),8.71–8.66(m,8H),7.95(dt,J＝7.9,0.8Hz,2H),7.39(s,7H),7.21(t,J＝7.9Hz,2H),7.18–7.11(m,2H),7.04(dt,J＝9.0,1.2Hz,1H),6.98–6.92(m,2H),6.92–6.77(m,4H),6.73(ddt,J＝9.0,7.9,1.0Hz,1H),6.56(dt,J＝7.9,1.1Hz,1H),6.45(s,4H),6.10(d,J＝0.9Hz,8H),4.51(dqd,J＝7.4,1.8,0.9Hz,1H),4.46–4.38(m,1H),4.21(td,J＝5.0,3.1Hz,4H),4.19–4.08(m,2H),4.03(td,J＝3.7,0.8Hz,4H),3.83(p,J＝4.7Hz,1H),3.78–3.55(m,14H),2.59(p,J＝6.3Hz,1H),1.94–1.59(m,9H),0.16(s,7H).13C NMR(125MHz,Chloroform-d)δ155.43,155.06,155.04,147.67,146.53,134.75,134.24,133.43,131.70,128.32,128.08,127.78,127.67,127.62,127.58,127.53,127.00,126.91,126.88,126.41,126.28,125.11,122.18,122.13,122.08,119.20,119.19,119.09,119.00,116.53,116.49,116.44,116.07,109.45,109.06,108.99,106.99,90.80,70.99,70.37,70.04,70.02,69.24,69.07,68.93,68.88,68.59,67.80,64.09,47.67,47.63,47.43,43.09,30.11,29.52,27.69.MS(ES):m/z(％):2229(100)[M + ].
(2) Preparation of vertical monomolecular film field effect control switch
The procedure of example 1 was repeated except that the compound A3 was used in place of the compound A1.
When the vertical monomolecular film field effect control switch is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, when the gate voltage is respectively-0.5V, 0V and 0.5V, the characteristic curves of the current changing along with the source drain voltage are respectively shown in fig. 10, 11 and 12, and according to the results shown in fig. 10-12, the source drain current is increased and the molecular conductivity is improved in the process of gradually increasing the source drain voltage from-2V to +2V; in the process that the source-drain voltage is gradually reduced from +2V to-2V, the source-drain current is reduced, and the molecular conductivity is reduced; the source-drain current increases when the gate voltage is ±0.5v with respect to the gate voltage of 0V. The temperature dependence was tested using a comprehensive testing system and found to be consistent throughout the range 248-303K. The result shows that the obtained vertical monomolecular film field effect control switch has strong regulation and control capability on molecular conductivity, has strong gate regulation and control capability, and can exist stably in an air environment.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modifications, equivalent substitutions, improvements, etc. that are within the spirit and principles of the present application are intended to be included within the scope of the present application.

Claims (11)

1. A vertical monomolecular film field effect control switch comprises [2]]A rotaxane molecule; said [2]]The rotaxane molecule consists of cyclic ions and linear molecules; the cyclic ion is CBPQT 4+ The structure is as follows:
Figure FDA0004094093630000011
the structural formula of the linear molecule is shown as formula A:
X 1 —Q 1 —R 1 —Q 2 —R 2 —Q 3 —X 2
formula A;
wherein X is 1 Selected from the group consisting of
Figure FDA0004094093630000012
Q 1 Is->
Figure FDA0004094093630000013
R 1 Selected from->
Figure FDA0004094093630000014
Q 2 Selected from->
Figure FDA0004094093630000015
Figure FDA0004094093630000016
R 2 Is->
Figure FDA0004094093630000017
Q 3 Is->
Figure FDA0004094093630000018
X 2 Is->
Figure FDA0004094093630000019
2. The vertical monolayer field effect control switch of claim 1, wherein the [2] rotaxane molecule is selected from any of A1-A3:
Figure FDA0004094093630000021
3. the vertical monomolecular film field effect control switch according to claim 1 or 2, wherein the vertical monomolecular film field effect control switch comprises a semiconductor base layer, a conductive metal source electrode, an insulating support layer, a self-assembled monomolecular film, a single-layer graphene drain electrode, a conductive metal gate electrode, and an ion gate electrode; the self-assembled monolayer is composed of the [2] rotaxane molecule.
4. A vertical monolayer field effect control switch according to claim 3, wherein the self-assembled monolayer has a thickness of 3-9nm.
5. The vertical monomolecular film field effect control switch according to claim 3, wherein the semiconductor material of the semiconductor base layer is selected fromFrom Si or GaAs; the insulating material of the insulating supporting layer is selected from SiO 2 、Si 3 N 4 Or GaS; the thickness of the insulating supporting layer is 80-120nm.
6. The vertical monomolecular film field effect control switch according to claim 3, wherein the metal materials of the conductive metal source electrode, the conductive metal drain electrode, and the conductive metal gate electrode are respectively selected from Cr/Au, cr/Ag, or Cr/Pt; the thickness of the metal material is (10-20 nm)/(50-100 nm) respectively.
7. A vertical monomolecular film field effect control switch according to claim 3, wherein said conductive metal source terminal electrode is circular with a diameter of 1-2 μm; the single-layer graphene drain electrode is round, and the diameter is 60-150 mu m; the conductive metal drain electrode is semi-circular, the outer diameter is 100-170 mu m, and the inner diameter is 60-120 mu m; the conductive metal gate electrode is semicircular, the outer diameter is 220-280 mu m, and the inner diameter is 180-240 mu m;
The single-layer graphene drain electrode completely covers the conductive metal source electrode; the ion grid completely covers the single-layer graphene drain electrode and the conductive metal drain electrode, and partially covers the conductive metal grid electrode.
8. The vertical monomolecular film field effect control switch according to claim 3, wherein the ion gate is a hydrogel material storing LiF, liCl or NaCl salt ions having a salt ion concentration of 1 x 10 -2 -1mol/L; the polymer monomer of the hydrogel material is selected from acrylic acid, acrylamide, vinyl alcohol, sodium styrene sulfonate or methacryloxyethyl trimethyl ammonium chloride.
9. A method of manufacturing a vertical monolayer field effect control switch according to any one of claims 1 to 8, comprising the steps of:
1) Preparing a semiconductor substrate layer and an insulating support layer, wherein the insulating support layer is an upper layer, and the semiconductor substrate layer is a lower layer;
2) Preparing a conductive metal gate electrode on the upper surface of the insulating support layer;
3) Preparing a round hole in the insulating supporting layer to expose a bottom semiconductor substrate, and preparing a conductive metal source electrode on the upper surface of the bottom semiconductor substrate;
4) Self-assembling the [2] rotaxane molecule and the conductive metal source end electrode to obtain a self-assembled monomolecular film; the self-assembled monomolecular film is composed of the [2] rotaxane molecules;
5) Completely covering the single-layer graphene on the top of the round hole to obtain a single-layer graphene drain electrode;
6) Preparing a conductive metal drain electrode at the outer side of the single-layer graphene drain electrode relative to the other side of the conductive metal gate electrode;
7) And covering an ion grid, wherein the ion grid completely covers the single-layer graphene drain electrode and the conductive metal drain electrode, and partially covers the conductive metal grid electrode.
10. The method of manufacturing of claim 9, wherein the self-assembling comprises:
dissolving the [2] rotaxane molecule in a solvent to prepare a molecular solution;
dissolving tetrabutylammonium fluoride in the same solvent as the molecular solution to prepare a deprotection solution;
mixing the molecular solution and the deprotection solution to obtain a mixed solution;
immersing the semi-finished device obtained in the step 3) into the mixed solution for 10-14h, taking out, washing and drying;
wherein the solvent is acetonitrile or acetone; in the molecular solution, the [2] ]The concentration of rotaxane molecules was 0.5X10 -3 -2×10 -3 mol/L; the concentration of tetrabutylammonium fluoride in the deprotected solution is 1X 10 -3 -3×10 -3 mol/L。
11. The preparation method of claim 9, wherein the conductive metal drain electrode and the conductive metal gate electrode are prepared by means of photolithography-vapor deposition of metal electrodes, respectively;
the conductive metal source electrode is prepared by magnetron sputtering coating, atomic layer deposition or vacuum evaporation coating, and is annealed in a gas of 200-300 ℃ for 1-2h, wherein the gas is argon or hydrogen;
the round holes in the insulating support layer are prepared in a photoetching-etching mode;
the single-layer graphene drain electrode is obtained by means of chemical vapor deposition-dry transfer or chemical vapor deposition-wet transfer.
CN202310160890.1A 2023-02-24 2023-02-24 Vertical monomolecular film field effect control switch and preparation method thereof Pending CN116217573A (en)

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