CN118234253B - Single-molecule field effect transistor based on double-gate regulation and control and preparation method thereof - Google Patents
Single-molecule field effect transistor based on double-gate regulation and control and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/481—Insulated gate field-effect transistors [IGFETs] characterised by the gate conductors
- H10K10/482—Insulated gate field-effect transistors [IGFETs] characterised by the gate conductors the IGFET comprising multiple separately-addressable gate electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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- Manufacturing & Machinery (AREA)
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- Carbon And Carbon Compounds (AREA)
- Thin Film Transistor (AREA)
Abstract
The invention relates to the technical field of semiconductor devices, in particular to a single-molecule field effect transistor based on double-gate regulation and control and a preparation method thereof, wherein the single-molecule field effect transistor based on double-gate regulation and control comprises: the device comprises a single-molecule field effect transistor and a top gate structure, wherein the top gate structure is assembled on the top of the single-molecule field effect transistor; the single-molecule field effect transistor comprises a graphene electrode and a single-molecule heterojunction formed by reacting a target molecule with an amino group at the tail end and a carboxylated graphene electrode. The preparation method of the single-molecule field effect transistor based on double-gate regulation comprises the preparation of the single-molecule field effect transistor and the top gate structure and the assembly process of the single-molecule field effect transistor and the top gate structure. The top gate and the single-molecule field effect transistor are separately prepared and then assembled in one step, so that the risk of damaging the device performance in the preparation process is avoided.
Description
Technical Field
The invention relates to the technical field of semiconductor devices, in particular to a single-molecule field effect transistor based on double-gate regulation and control and a preparation method thereof.
Background
Under the push of moore's law, the semiconductor industry is continually pursuing transistor size scaling to achieve higher integration and better performance. Furthermore, with the development of nanoscience and technology, researchers have focused on microscopic-scale electronic devices, especially single-molecule devices that control electronic properties at the molecular level. These efforts are directed to the trend of future high performance electronic devices and have revealed a continuing need for advanced microelectronic technologies in the marketplace.
Currently, with further reduction of transistor size, conventional single gate field effect transistors face a number of short-channel effect challenges, such as a decrease in threshold voltage and an increase in leakage current, which limit further improvement of device performance. To address these challenges, dual gate field effect transistors (DG-FETs) have been developed to achieve more efficient channel control through a top and bottom dual gate design, significantly improving the device switching ratio and leakage current issues. However, in the study of Single-Molecule Field effect transistors (Single-Molecule Field-Effect Transistor, SMFET), particularly those using fragile two-dimensional materials as conductive channels, the problem of material property deterioration is still faced in the conventional manufacturing process. For example, the steps of photolithography and vacuum deposition, which are common in the preparation process of the top gate insulating dielectric layer in the prior art, may damage the contact interface of the material, and reduce the overall device performance.
Therefore, how to provide a single-molecule field effect transistor based on dual-gate regulation and control and a preparation method thereof, so as to avoid damaging a contact interface in the process of preparing the transistor and improve the performance stability of the transistor is a technical problem to be solved at present.
Disclosure of Invention
The present invention is directed to solving at least one of the technical problems existing in the related art. To this end, a first object of the present invention is to provide a single-molecule field effect transistor based on dual gate regulation; the second object of the invention is to provide a preparation method of a single-molecule field effect transistor based on double-gate regulation.
In order to achieve the first object, the invention adopts the following technical scheme:
A single-molecule field effect transistor based on dual gate modulation, comprising:
The device comprises a single-molecule field effect transistor and a top gate structure, wherein the top gate structure is assembled on the top of the single-molecule field effect transistor;
The single-molecule field effect transistor comprises a back gate, a back gate insulating dielectric layer, a graphene electrode and a single-molecule heterojunction formed by single target molecules, wherein the back gate insulating dielectric layer, the graphene electrode and the single-molecule heterojunction are sequentially arranged on a back gate substrate, and the single-molecule heterojunction is formed by reacting target molecules with amino groups at the tail ends and the graphene electrode carboxylated at the tail ends;
the top gate structure includes a top gate and a top gate insulating dielectric layer disposed under the top gate.
Further, a metal source electrode and a metal drain electrode are respectively arranged at two ends of the graphene electrode.
Further, the top gate is a metal top gate.
Further, the back gate is a P + -Si back gate.
Further, the graphene electrode gap is adapted to the target molecule length.
Further, the structural formula of the target molecule is as follows:
。
in order to achieve the second object, the invention adopts the following technical scheme:
the preparation method of the single-molecule field effect transistor based on double-gate regulation is used for preparing the single-molecule field effect transistor based on double-gate regulation, and comprises the following steps:
S100, preparing a single-molecule field effect transistor;
s200, preparing a top gate structure;
S300, assembling the prepared top gate structure on the top of the single-molecule field effect transistor through a one-step method, and preparing the single-molecule field effect transistor based on double-gate regulation.
Further, S100 includes the following steps:
S110, preparing a target molecule;
s120, preparing a graphene electrode with two ends respectively being a metal source electrode and a metal drain electrode;
S130, carrying out terminal carboxylation on the prepared graphene electrode to prepare a graphene electrode containing carboxyl functional groups;
And S140, enabling the target molecule and the graphene electrode containing the carboxyl functional group to generate covalent bond connection reaction to form a single-molecule heterojunction, and preparing the single-molecule field effect transistor.
Further, S120 includes the following steps:
s121, preparing a back gate substrate;
s122, preparing a gold mark on the prepared back gate substrate, and preparing a silicon substrate with the gold mark;
S123, etching the silicon substrate with the gold mark by using plasma to prepare the silicon substrate with the graphene;
s124, preparing a graphene electrode with metal electrodes at two ends by using a silicon substrate with graphene.
Further, the preparation of the top gate in S200 includes the following steps:
s210, preparing a sacrificial layer growth substrate;
S220, preparing a graphene substrate;
S230, preparing a top gate substrate, preparing a patterned mask on the substrate covered with the single-layer graphene through photoetching, and then depositing a top gate insulating dielectric layer film;
and S240, preparing the metal top gate on the substrate covered with the top gate and the graphene substrate through photoetching and thermal evaporation.
Further, the double-gate-controlled single-molecule field effect transistor prepared in S300 was annealed at 150 ℃ for 2 hours.
Further, in S130, the end carboxylated graphene electrode is prepared by oxidizing modification of the carboxyl functional groups at the edges of the graphene electrode by an all dry method of carbon dioxide gas oxidation.
The above technical solutions in the embodiments of the present invention have at least one of the following technical effects:
According to the technical scheme provided by the invention, the top gate structure and the single-molecule field effect transistor are respectively and independently prepared and then assembled, so that the complex process of directly carrying out on a fragile two-dimensional material is avoided, and the damage to a molecular conducting channel in the manufacturing process is effectively reduced, so that the inherent characteristics and performance of the device are maintained. In addition, the double-gate design not only improves the accuracy of current control, but also more uniformly and effectively adjusts the energy level of a single molecule through the synergistic effect of the top gate and the bottom gate, further improves the performance and the energy efficiency of the device, and provides a new thought for improving the performance of the single-molecule field effect transistor after integration;
Second, the single-molecule field effect transistor based on double-gate regulation provided by the invention can regulate the output voltage of the single-molecule field effect transistor through the electrical characteristics of double-gate voltage, bias voltage and the like, so as to realize the regulation of devices;
Thirdly, the single-molecule field effect transistor based on double-gate regulation, provided by the invention, can be used for researching the charge transmission behavior of single molecules. By introducing target molecules between the electrodes of the transistor, the transmission condition of molecular charge carriers can be observed, so that the electronic properties and the transmission mechanism of the molecules are deeply known; the-NH 2 at two ends of the target molecule and the-COOH at the tail end of the graphene point electrode form an amide covalent bond to be bridged, a conductive channel based on the graphene single-molecule field effect transistor is constructed, a double-gate structure of a top gate and a back gate is prepared, the energy level positions of the molecules can be regulated and controlled more uniformly and more effectively by the upper gate and the lower gate, the relative positions of the energy level of the molecules and the fermi level of the electrode are changed, and the conductive characteristic of the molecules is regulated and controlled, so that more accurate control of current is realized.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is a schematic structural diagram of a single-molecule field effect transistor based on dual-gate regulation according to the present invention.
Fig. 2 is a preparation flow chart of a single-molecule field effect transistor based on double-gate regulation and control.
Fig. 3 is a flowchart of a preparation of a single-molecule field effect transistor according to an embodiment of the present invention.
Fig. 4 is a graph showing output characteristics of a single-molecule field effect transistor according to an embodiment of the present invention, wherein the current varies with bias voltage when the gate voltages are 4V, 3V, 2V, 1V, and 0V, respectively.
Fig. 5 is a preparation flow chart of a top gate structure according to an embodiment of the present invention.
Fig. 6 is a characteristic diagram of a single-molecule field effect transistor with a bias voltage variation according to a gate voltage of 1V according to an embodiment of the present invention.
Fig. 7 is a graph showing a transfer characteristic of a single-molecule field effect transistor according to an embodiment of the present invention, wherein the single-molecule field effect transistor is based on dual-gate regulation, and the current is changed along with the gate voltage when the bias voltage is 0.1V.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The following examples are illustrative of the invention but are not intended to limit the scope of the invention.
In the following examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are commercially available.
According to an embodiment of the present invention, a single-molecule field effect transistor based on dual-gate regulation, as shown in fig. 1, includes:
The device comprises a single-molecule field effect transistor and a top gate structure, wherein the top gate structure is assembled on the top of the single-molecule field effect transistor;
The single-molecule field effect transistor comprises a back gate, a back gate insulating dielectric layer, a graphene electrode (not shown) and a single-molecule heterojunction, wherein the back gate insulating dielectric layer, the graphene electrode (not shown) and the single-molecule heterojunction are sequentially arranged on a back gate substrate (not shown), and the single-molecule heterojunction is formed by the reaction of a target molecule with an amino group at the tail end and a graphene electrode carboxylated at the tail end;
the top gate structure includes a top gate and a top gate insulating dielectric layer disposed under the top gate.
According to one embodiment of the present invention, two ends of the graphene electrode are respectively provided with a metal source electrode and a metal drain electrode.
According to a specific embodiment of the present invention, the top gate is a metal top gate.
According to a specific embodiment provided by the invention, the top gate is a Cr/Au top gate.
According to a specific embodiment provided by the invention, the back gate is a P + -Si back gate.
According to a specific embodiment of the present invention, the substrate of the back gate and the substrate of the top gate are both silicon substrates.
According to a specific embodiment provided by the invention, the graphene electrode gap is adapted to the target molecule length.
According to one embodiment of the present invention, the structural formula of the target molecule is as follows:
。
The preparation method of the single-molecule field effect transistor based on double-gate regulation is further described below with reference to specific embodiments, and the preparation flow of the single-molecule field effect transistor based on double-gate regulation is shown in fig. 2.
Examples
1. The preparation flow of the single-molecule field effect transistor is shown in fig. 3, and the specific preparation process is as follows:
The preparation of the target compound comprises the following steps:
step one, preparation of a compound 1:
10-bromoanthracene-9-amine is added into a50 mL two-mouth bottle in sequence under the protection of N 2 (0.95 G,3.5 mmol), THF (20 mL), di-tert-butyl dicarbonate (0.87 g,4.0 mmol), triethylamine (0.932 mL,6.8 mmol) and stirring overnight at room temperature. After the completion of the reaction, the mixture was extracted with ethyl acetate (ETHYL ACETATE, EA), washed three times with water, dried over anhydrous Na 2SO4 after removing the bottom aqueous phase, and subjected to column chromatography after removing the solvent (EA) by rotary evaporation to give Compound 1。
Step two, preparation of a compound 2:
to a 50 mL two-necked flask was added compound 1 (0.47 g,1.27 mmol), anhydrous potassium acetate (0.372 g,3.8 mmol), B 2（pin）2（0.48g,1.9 mmol）,PdCl2 (dppf) (0.028 g,0.03 mmol) and 20mL of anhydrous dioxane in this order under N 2. The mixture was reacted at 100℃for 12 hours. Cooling to room temperature after the reaction, suction filtering, extracting filtrate with EA, washing with water (EA is insoluble in water), washing with saturated sodium chloride, removing bottom water phase, drying with anhydrous Na 2SO4, rotary evaporating to remove solvent (EA), and separating by column chromatography to obtain compound 2 Compound 2 was a white solid.
Step three, preparing a compound 3:
compound 2 (0.419 g,1.00 mmol), K 2CO3 (0.140 g,1.08 mmol), 9, 10-dibromoanthracene were added sequentially to a 50mL two-necked flask under N 2 protection (0.333 G,0.99 mmol) Pd (PPh 3)4 (0.046 g,0.04 mmol), and then 20 mL (volume ratio: 4:1) as a mixed solvent of ethylene glycol dimethyl ether and water were added thereto, the mixture was reacted at 85℃to 8: 8h, cooled to room temperature, and the solvent was removed under reduced pressure, water 10: 10 mL was added to the reaction mixture, extracted with DCM, the organic phases were combined, and the solvent was removed by rotary evaporation after drying over anhydrous sodium sulfate, followed by column chromatography to give Compound 3。
Step four, preparing a compound 4:
To a 50 mL two-necked flask was added compound 3 (0.497 g,1.11 mmol), tetrakis (triphenylphosphine) palladium (0.155 g,1.20 mmol) under N 2 protection, and then anhydrous acetonitrile 20mL was added thereto, followed by stirring for 30 minutes and cooling to 10 ℃. Copper iodide (0.57 g,3.60 mol) was added and the resulting suspension was stirred at 20℃for a further 2.5 hours and finally at 60℃for 3 hours. The mixture was then left at room temperature overnight and filtered to give compound 4 。
Step five, preparing a compound 5:
To a 50mL two-necked flask was added, in order, compound 4 (0.517g, 1.11 mmol), potassium carbonate (0.245 g,1.78 mmol) dissolved in 10mL THF/MeOH (1:1) and stirred at room temperature for 6: 6 h under N 2 protection, and the reaction was completed and the solid was filtered. Washing with DCM for several times, removing solvent under reduced pressure, and purifying by column chromatography to obtain compound 5 。
Step six, preparing a target compound:
To a 50 mL two-necked flask under N 2 was successively added Compound 5 (0.404 g,1.03 mmol), cuI (0.190 g,1.00 mmol), pt (PPh 3)2Cl2 (0.793 g,1.01 mmol), triethylamine (TRIETHYLAMINE, abbreviated as TEA) (2 mL, in an alkaline atmosphere), dissolved in 10mL of chloroform solution, stirred at room temperature for 4 hours, the reaction was completed, and the solid was obtained by filtration, washed with chloroform to obtain the objective compound 。
And (II) preparing a graphene electrode with two ends respectively being a metal source electrode and a metal drain electrode, comprising the following steps:
Step one, preparing a back gate substrate:
A P-doped silicon wafer (P-Si/SiO 2) with the thickness of 300nm of SiO 2 is taken as a substrate, and is cut into a size of 1cm multiplied by 1cm, wherein P-Si/SiO 2 is a back gate insulating dielectric layer.
Soaking the silicon wafer in a piranha solution, wherein the volume ratio of the H 2O2 with the concentration of 35% to the concentrated H 2SO4 is 3:7, heating and cleaning for 5 hours at 110 ℃, adding ultrapure water, performing ultrasonic treatment for 10 minutes, and repeatedly cleaning residual acid on the silicon wafer for 4-5 times.
And sequentially placing the silicon wafer in acetone, ethanol and ultrapure water, respectively ultrasonically cleaning for 10min, and then drying with nitrogen for standby.
Preparing a gold mark on the prepared back gate substrate, and preparing a silicon substrate with the gold mark:
The silicon substrate is adsorbed on a spin table of a spin coater, and the preset rotating speed is 650r/min, the time is 6s, the positive rotating speed is 4000r/min, and the time is 45s. Photoresist with the model AR-P5350 ALLRESIST is spin-coated on a silicon substrate, and then the silicon substrate is put on a heating table at 110 ℃ for baking for 3min, so that the photoresist is solidified into a film.
The silicon substrate was placed under a mask plate with a pattern of positional coordinate marks ("ten" and digital marks) for uv exposure for 20s. The exposed silicon substrate is soaked in a developing solution formed by mixing a solution of AR300-36 developing solution and deionized water, and the mixing ratio of the AR300-36 developing solution to the deionized water is about 7:1, developing for 12s, then soaking in deionized water for fixing for 15s, then flushing the silicon substrate with deionized water, and then drying with nitrogen, wherein the exposed position coordinate pattern can be exposed on the silicon substrate.
And preparing a gold mark on the exposed position coordinate pattern on the silicon substrate by utilizing a thermal evaporation coating instrument, and thermally evaporating a metal chromium (Cr) layer with the thickness of 8nm on the silicon substrate to ensure that the subsequent gold layer is better attached to the silicon substrate. Then switching the evaporated metal source, and thermally evaporating a metal gold (Au) layer with the thickness of 60nm on the silicon substrate. And taking out the silicon substrate after cooling after evaporation, and soaking the silicon substrate by using an acetone solution to remove the metal coating with the photoresist part, so that only the metal position coordinate pattern mark exists on the silicon substrate. And cleaning the silicon substrate with the gold mark in the isopropanol, acetone, deionized water and ethanol for 10min respectively, and then drying with nitrogen for standby.
Step three, etching the silicon substrate with the gold mark by using plasma to prepare the silicon substrate with the graphene;
selecting a plurality of Kish graphite flakes with the size of about 2-3 mm, arranging the Kish graphite flakes into a row, sequentially adhering the Kish graphite flakes to one end of a cut transparent adhesive tape with the length of about 8cm, and repeatedly folding the adhesive tape to uniformly distribute the graphite flakes on the adhesive tape.
In order to reduce oxygen dangling bonds on the silicon substrate, the graphene sample is attached to the silicon substrate, and the silicon substrate with the gold mark prepared above is etched for 30 seconds by using oxygen plasma with the power of 50W.
And (3) reversely buckling the surface of the silicon substrate on the adhesive tape which is adhered with graphite, heating the whole on a heating table at 110 ℃ for 3min, and then slowly removing the silicon substrate from the adhesive tape. And (3) placing the silicon substrate with the graphene in an optical microscope, searching a graphene sample with more than 3 layers for preparing a graphene electrode in a subsequent experiment according to the optical contrast relation between the graphene sample and the silicon substrate, and recording a 20-time optical diagram of a gold mark position corresponding to the graphene sample with more than 3 layers and more than 15 mu m in size on the silicon substrate for searching in a subsequent experimental process.
To remove the tape residue on the graphene sample and the silicon substrate, the silicon substrate with the graphene sample was annealed in 500 ℃ hydrogen for 2h.
Preparing a graphene electrode with metal electrodes at two ends by using a silicon substrate with graphene:
The matlab program is used for carrying out angle correction on a 100-time optical diagram of the graphene sample with the function.
And then, taking the corrected sample photo as a reference object, and importing the corrected sample photo into AutoCAD software to draw a metal electrode pattern. Wherein, the side length of the rectangular metal electrode is 200 μm×250 μm, the horizontal and vertical distances between 4 small cross-shaped metal marks (the field calibration marks used in the electron beam lithography) around the graphene sample are 40 μm, and the parallel metal electrode spacing is 15 μm.
The drawn metal electrode pattern is imported into DY2000A software, and the size of an exposure field, an exposure layer and an exposure sequence are set. A file for subsequent Electron Beam Lithography (EBL) is then derived.
And (3) adsorbing the silicon substrate on a rotary table of a spin coater, and performing spin coating on the electron beam photoresist twice. The method comprises the steps of setting the preset rotating speed to 650r/min for the first time, setting the positive rotating speed to 4500r/min for 6s and setting the positive rotating speed to 45s, spin-coating the model PMMA 495 photoresist on a silicon substrate, and then placing the silicon substrate on a heating table at 180 ℃ for baking for 2min to enable the photoresist to be solidified into a film. Setting the preset rotating speed at 650r/min for 6s and the positive rotating speed at 4000r/min for 45s for the second time, spin-coating the model PMMA 950 photoresist on the silicon substrate, and then placing the silicon substrate on a heating table at 180 ℃ for baking 2min to solidify the photoresist into a film.
And etching the silicon substrate coated with the double-layer PMMA glue by using an electron beam exposure system, wherein exposure parameters are respectively set to be 25kV of electron beam high voltage, 2.42nA of beam current and 400 mu C/cm 2 of electron beam dose. And exposing on the double-layer PMMA photoresist according to the pre-drawn metal electrode pattern file. The exposed silicon substrate is soaked in a developing solution formed by mixing isopropanol and methyl isobutyl ketone (the mixing volume ratio of the isopropanol to the methyl isobutyl ketone is about 3:1) for development, the development time is 12s, then the silicon substrate is soaked in the isopropanol for fixation for 10s, the organic solution remained on the surface of the silicon substrate is washed by ethanol and then dried by nitrogen, and the exposed metal electrode pattern can be exposed on the silicon substrate.
The metal electrode pattern exposed on the silicon substrate is prepared into a metal electrode by utilizing a thermal evaporation coating instrument, and a metal chromium (Cr) layer with the thickness of 8nm is thermally evaporated on the silicon substrate, so that the subsequent gold layer is better attached to the silicon substrate. Then switching the evaporated metal source, and thermally evaporating a metal gold (Au) layer with the thickness of 60nm on the silicon substrate. And taking out the silicon substrate after the evaporation is cooled, and evaporating SiO 2 with the thickness of 40nm by using an electron beam evaporator as a protective layer of the metal electrode. And taking out the silicon substrate after the evaporation is cooled, and soaking the silicon substrate in acetone solution to remove the metal coating with the photoresist part, so that only the metal electrode exists on the silicon substrate. And cleaning the prepared silicon substrate with the metal electrode in isopropanol, acetone, deionized water and ethanol for 10min respectively, and then drying by nitrogen.
Pre-etching graphene: by utilizing the anisotropic etching effect of graphene in hydrogen plasma, after circular array defect sites are artificially introduced on the graphene, the hydrogen plasma etching can enable the circular defect sites on the graphene to be changed into hexagonal holes with saw-tooth edges (zigzag). By designing a defect site pattern and utilizing a hydrogen plasma anisotropic etching principle, the opposite vertex angles of two adjacent hexagonal etching holes can be controlled on graphene, and the angles become gradually larger until the adjacent hexagonal etching holes are connected in a continuous slow etching process, so that a graphene triangle electrode pair which has no obvious defect, has a clear zigzag edge configuration and has a nano-scale spacing is finally formed, and a subsequent reaction site for connection with a single molecule is provided.
The top end of the graphene triangle electrode pair is precisely aligned, the lattice direction of anisotropic etching of graphene is required to be known in advance, an artificial defect round hole with the same lattice direction is manufactured through the direction, and according to defect introduction in the direction, a point aligned graphene triangle electrode pair with a perfect configuration can be manufactured. The process of obtaining the anisotropically etched graphene lattice direction in advance is a pre-etching stage, and the specific flow is as follows: photographing and storing a graphene sample under a 100-time optical microscope, and performing angle correction on a 100-time optical diagram of the graphene sample by using a matlab program with functions; and then, taking the corrected sample photo as a reference object, and introducing the corrected sample photo into AutoCAD software to draw a graphene pre-etching pattern. The aperture of the round hole in the pre-etched array pattern is 0.1 μm, and the rectangular size is 4 μm×0.5 μm; and importing the drawn graphene pre-etching pattern into DY2000A software, and setting the size of an exposure field, an exposure layer and an exposure sequence. Then deriving a file for subsequent Electron Beam Lithography (EBL); and (3) adsorbing the silicon substrate on a spin table of a spin coater, and coating electron beam photoresist. Setting the preset rotating speed to 650r/min, the positive rotating speed to 4000r/min and the time to 45s, spin-coating the model PMMA 950 photoresist on the silicon substrate, and then placing the silicon substrate on a heating table at 180 ℃ for baking for 2min to solidify the photoresist into a film; Etching the silicon substrate of the spin-coated PMMA photoresist by using an electron beam exposure system, wherein exposure parameters are respectively set to be 30kV of electron beam high voltage, 0.134nA of beam current and 400 mu C/cm 2 of electron beam dose; and exposing on the PMMA photoresist according to the pre-drawn graphene pre-etching pattern file. The exposed silicon substrate is soaked in a developing solution formed by mixing isopropanol and methyl isobutyl ketone (the mixing volume ratio of the isopropanol to the methyl isobutyl ketone is about 3:1) for development, the development time is 5s, then the silicon substrate is soaked in the isopropanol and fixed for 10s, the organic solution remained on the surface of the silicon substrate is washed by ethanol and then dried by nitrogen, and the exposed graphene pre-etched pattern can be exposed on the silicon substrate; And placing the silicon substrate in an oxygen plasma etcher to etch the graphene pre-etching array, and artificially manufacturing defect sites of subsequent hydrogen plasma etching. The etching cavity pressure is 3Pa, the oxygen flow is 50sccm, the radio frequency power is 50W, and the etching time is 50s. After etching, placing the silicon substrate in acetone to soak and remove PMMA photoresist residual gum, and then washing the silicon substrate with acetone, and drying the silicon substrate with nitrogen; graphene with artificially introduced pre-etched defect sites (circular hole array) is placed in a hydrogen plasma etching system to etch the hexagonal pattern. The etching temperature was set at 500℃and the distance from the center of the glow zone generating the plasma to the center of the silicon substrate was adjusted to 45cm, and the flow rate of hydrogen gas was controlled to about 12sccm. And 3 times of hydrogen cleaning is carried out on the reaction cavity before pre-etching so as to remove other residual gases in the tube. The etching power was set at 18W and the reaction time was 2h. And after the pre-etching is finished, slowly cooling to room temperature, and taking out the silicon substrate. And (3) recording a graphene pre-etching electron image under at least 6 ten thousand times by using a scanning tunneling electron microscope (SEM), introducing the graphene pre-etching SEM image into AutoCAD software, selecting an angle measuring tool in the software, measuring the angle of the hexagon for multiple times, and averaging to obtain an average angle value which is the anisotropic etching lattice direction of the graphene sample.
Graphene is positively etched: the positive etching process is the final step of preparing the triangular dot electrode pair, and is to etch triangular graphene electrodes with precisely aligned peaks in the graphene channels between the gold electrodes. And according to the anisotropic lattice direction of the graphene determined by the pre-etching in the previous step, a plurality of round holes with the same lattice direction of the graphene are manufactured in the channel by adopting electron beam Exposure (EBL). Drawing circular holes in DY2000A software, wherein the diameter of the designed holes is 75nm, the center distance between adjacent holes is 400nm, and determining the exposure sequence of patterns; and (3) adsorbing the silicon substrate on a spin table of a spin coater, and coating electron beam photoresist. Setting the preset rotating speed to be 650 r/min, the time to be 6 s, the positive rotating speed to be 4000 r/min and the time to be 45 s, spin-coating the model PMMA 950 photoresist on the silicon substrate, and then placing the silicon substrate on a heating table at 180 ℃ to bake for 2min to solidify the photoresist into a film; etching the silicon substrate of the spin-coated PMMA photoresist by using an electron beam exposure system, wherein exposure parameters are respectively set to be 30kV of electron beam high voltage, 0.134nA of beam current and 400 mu C/cm 2 of electron beam dose; and exposing on the PMMA photoresist according to the pre-drawn graphene positive etching pattern file. Soaking the exposed silicon substrate in a developing solution formed by mixing isopropanol and methyl isobutyl ketone (the mixing volume ratio is about 3:1) for development for 5s, then soaking in isopropanol for fixation for 10s, flushing the organic solution remained on the surface of the silicon substrate with ethanol, and then drying with nitrogen, so that the exposed graphene positive etching pattern can be exposed on the silicon substrate; and placing the silicon substrate in an oxygen plasma etching instrument to etch the graphene positive etching pattern, wherein the etching cavity pressure is 3Pa, the oxygen flow is 50sccm, the radio frequency power is 50W, and the etching time is 50s. After etching, placing the silicon substrate in acetone to soak and remove PMMA photoresist residual gum, and then washing the silicon substrate with acetone, and drying the silicon substrate with nitrogen; before the positive etching of graphene, respectively binding two source electrodes and two drain electrodes of an Agilent 4155C semiconductor tester on two metal electrodes of a graphene sample to test and record initial current of a graphene channel, and pre-judging parameters such as hydrogen plasma positive etching time of a subsequent graphene channel according to past experimental experience; and placing the silicon substrate in a hydrogen etching system for positive etching, wherein the etching conditions are consistent with those of the pre-etching. Monitoring the etching endpoint using electrical means: along with the progress of etching, adjacent hexagonal graphene holes are gradually close to each other, the graphene conductive area is gradually narrowed, the resistance of the device is gradually increased, and the current is gradually reduced until an open circuit is formed. And (3) etching for multiple times, measuring a current value after each etching, and controlling the next etching time according to the change of the current until the etching is completed, wherein the graphene triangle electrode pair forms an open circuit. The corresponding etching time is controlled, and the nano-scale graphene electrode spacing equivalent to the molecular size can be obtained.
When the gap between the graphene triangle electrode pair generated after hydrogen plasma etching is smaller than 5nm, tunneling current is generated, and the graphene triangle electrode pair cannot be directly characterized by means of a scanning electron microscope, an atomic force microscope and the like, and the graphene triangle electrode pair can be firstly simulated by utilizing Simmons tunneling, fit an I-V curve and estimate the electrode gap so as to enable the electrode gap to be matched with molecules with different lengths at critical end points:
In the method, in the process of the invention, As a result of the electron tunneling area,Is the charge of the electrons and is,To a reduction of the planck's constant,For the insulator barrier height,Is the gap between the graphene electrode pair,Is the mass of the electrons and,Is the applied voltage. In the experiment, a certain bias voltage is applied to the metal electrodes at two ends of the graphene electrode, a corresponding current value is measured, and the current value is compared with the current value estimated by fitting to push out the corresponding gap size. The method can control the fit between the graphene electrode spacing and the actual molecular length after hydrogen plasma. The size of the graphene electrode gap can be precisely controlled by a remote hydrogen plasma etching method, so that the graphene triangular point electrode with an atomic-level clear edge configuration and adjustable gaps is prepared.
(III) carrying out terminal carboxylation on the prepared graphene electrode to prepare a graphene electrode containing carboxyl functional groups:
After constructing a graphene electrode gap adapted to the molecular length, an amide covalent reaction is performed on the target molecule with an amino end and a graphene end site with a carboxyl functional group to form a stable covalent bond connection.
Therefore, firstly, the edge of the graphene electrode needs to be subjected to oxidative modification of carboxyl functional groups, the oxidation is performed in a full dry mode through carbon dioxide gas oxidation, a silicon substrate with a graphene triangular electrode pair is placed in the central position of a temperature control area of a tubular furnace, the oxidation temperature is set to be 200 ℃, and the flow rate of the carbon dioxide gas is set to be about 50sccm. And 3 times of carbon dioxide gas cleaning is carried out on the reaction cavity before oxidation so as to remove other residual gases in the tube. The reaction time was 2h. And after the reaction is finished, slowly cooling to room temperature, and taking out the silicon substrate to obtain the graphene triangle electrode with carboxyl functional groups.
And (IV) carrying out covalent bond connection reaction on the target molecule and the graphene electrode containing carboxyl functional groups to form a single-molecule heterojunction, so as to prepare the single-molecule field effect transistor:
An amide covalent linking reaction is performed between a molecule having an amino terminus and a graphene electrode having a carboxyl functional group. The reaction took place in anhydrous and anaerobic glass bottles, an iron stand was removed and placed in a fume hood, and a double-necked flat bottom flask was again removed and fixed to the iron stand. And taking out a two-way exhaust pipe and a glass plug to be fixed at the upper port of the double-mouth flat-bottomed flask, sealing, and putting the dried silicon wafer into the double-mouth flat-bottomed flask from the other side port. A1 mg target molecule, 0.1g of 1- (3-dimethylaminopropyl) -3-2-ethylcarbodiimide hydrochloride catalyst, was poured into the two-necked flat-bottomed flask from the side port, and the side port was then closed with a cork. After all ports are closed, the double-mouth flat-bottomed flask can be vacuumized for about 30min, then the vacuum valve is closed, and the whole closed double-mouth flat-bottomed flask can reach a stable vacuum state. 10ml of anhydrous pyridine was sucked up by a syringe, and the soft stopper hole at the side port was filled into a two-necked flat bottom flask. The balloon was removed and inflated with the appropriate amount of nitrogen, the balloon inlet was secured to the end of the syringe remote from the needle tip and sealed and allowed to stand for 48 hours. In a sealed environment, the pyridine solvent gradually dissolves target molecules, and finally the molecules in the solution and the edges of the graphene electrodes are subjected to amide covalent connection reaction, so that the molecules are connected with the electrodes. And taking out the silicon substrate after 48 hours, sequentially taking a proper amount of acetone and deionized water to flush the silicon wafer for 3 times in order to remove the residual organic solution on the silicon substrate, and then drying by using nitrogen to prepare the single-molecule field effect transistor.
Electrical testing of single molecule field effect transistor connection: the connection and electrical properties of the single-molecule field effect transistor were tested by means of an ST-500 probe station and an Agilent 4155C semiconductor parameter. Two source and drain electrodes of an Agilent 4155C semiconductor tester are respectively bundled on two metal electrodes of a graphene sample to check the connection condition of a single-molecule field effect transistor, whether the device is successfully connected is judged through an IV test curve under the bias voltage range of +/-1V, and the characteristic diagram of the current of the single-molecule field effect transistor when the grid voltage is respectively 4V, 3V, 2V, 1V and 0V along with the bias voltage is shown in figure 4.
2. The preparation of the top gate structure is shown in fig. 5, and the preparation process comprises the following steps:
1. preparing a sacrificial layer growth substrate:
Taking an undoped pure silicon wafer (Si/SiO 2) with the thickness of 300nm of SiO 2 as a substrate for growing a graphene sacrificial layer, and cutting into the size of 1 cm multiplied by 1 cm; soaking a silicon wafer in a piranha solution (the volume ratio of H 2O2 with the concentration of 35% to concentrated H 2SO4 is 3:7), heating and cleaning for 5H at 110 ℃, adding ultrapure water, performing ultrasonic treatment for 10min, and repeatedly cleaning residual acid on the silicon wafer for 4-5 times; and sequentially placing the silicon wafer in acetone, ethanol and ultrapure water, respectively ultrasonically cleaning for 10min, and then drying with nitrogen for standby.
2. Preparing a graphene substrate:
Monolayer graphene is prepared on a silicon substrate by Chemical Vapor Deposition (CVD).
3. Preparing a top gate substrate:
a patterned mask is prepared by photolithography on a substrate covered with a single layer of graphene, and a top gate insulating dielectric layer film is deposited, for example, the top gate insulating dielectric layer may be any one of yttria, alumina, and hafnium oxide.
4. Preparing a metal top gate on the top gate covered substrate and the graphene substrate by photoetching and thermal evaporation:
Stripping and removing the single-layer graphene sacrificial layer on the lower surface of the top gate structure: and lightly stripping the top gate, the top gate insulating dielectric layer and the single-layer graphene sacrificial layer on the silicon substrate by using a polymethyl methacrylate (Polymethyl Methacrylate, PMMA) film, attaching the PMMA surface to a Polydimethylsiloxane (PDMS) seal, and removing the exposed single-layer graphene sacrificial layer after oxygen plasma etching treatment.
3. Preparing a single-molecule field effect transistor based on double-gate regulation:
The prepared top gate structure is transferred and stacked onto the prepared single-molecule field effect transistor by a one-step method, and the specific preparation process is as follows:
In a dry and anaerobic glove box environment, the stripped top gate structure is accurately aligned and transferred to a target material through a 100-time optical microscope, a single-molecule field effect transistor based on double-gate regulation is prepared, and the prepared single-molecule field effect transistor based on double-gate regulation is annealed for 2 hours at the temperature of 150 ℃ so as to improve the quality of a contact surface and the performance of a device.
Performance test of single-molecule field effect transistor based on double-gate regulation: the electrical properties of the devices were tested by the ST-500 probe station and Agilent4155C semiconductor parameter. Two source and drain electrodes of the Agilent4155C semiconductor tester are respectively tied on two metal source and drain electrodes of the graphene single-molecule field effect transistor, and two grid electrodes of the Agilent4155C semiconductor tester are respectively tied on a top grid and a back grid of the graphene single-molecule field effect transistor, so that performance test is performed on the device, and test results are shown in fig. 6 and 7.
By respectively introducing the grid electrodes at the upper side and the lower side of the transistor, the flow of carriers in the channel can be controlled more effectively, the leakage current can be reduced, and the energy consumption can be reduced; the device can be provided with better current control and better switching ratio is realized; in addition, the top grid can play a role in shielding, can reduce the interference of an external electric field and noise, and has a higher switching ratio.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (4)
1. The preparation method of the single-molecule field effect transistor based on double-gate regulation is characterized in that the single-molecule field effect transistor based on double-gate regulation comprises a single-molecule field effect transistor and a top gate structure, wherein the top gate structure is assembled at the top of the single-molecule field effect transistor, and the preparation method comprises the following steps:
s100, preparing a single-molecule field effect transistor to obtain a back gate structure;
s200, preparing a top gate structure;
S300, assembling the prepared top gate structure on the top of a single-molecule field effect transistor through a one-step method, and preparing the single-molecule field effect transistor based on double-gate regulation;
Wherein, the preparation process of the one-step method is as follows: in a glove box environment without water and oxygen, aligning and transferring the stripped top gate structure to a single-molecule heterojunction through an optical microscope, preparing a single-molecule field effect transistor based on double-gate regulation, and annealing the prepared single-molecule field effect transistor based on double-gate regulation at a temperature of 150 ℃ to improve the quality of a contact surface and the performance of a device.
2. The method of claim 1, wherein S100 comprises the steps of:
s110, preparing a target compound with an amino terminal;
s120, graphene pre-etching and graphene positive etching are included;
The process of the graphene pre-etching is as follows: utilizing the anisotropic etching effect of graphene in hydrogen plasma, after introducing circular array defect sites on the graphene, performing hydrogen plasma etching to enable the circular defect sites on the graphene to be changed into hexagons with saw-tooth edges, controlling the opposite vertex angles of two adjacent hexagons to etch holes on the graphene, gradually increasing until being connected in the continuous slow etching process, and finally forming a graphene triangle electrode pair which is a reaction site for connecting single molecules;
the process of graphene positive etching is as follows: the condition of the positive etching of the graphene is consistent with the condition of the pre-etching of the graphene, adjacent hexagonal graphene holes are gradually close to each other along with the progress of etching, the graphene conductive area is gradually narrowed, the resistance of the device is gradually increased, and the current is gradually reduced until a circuit breaker is formed;
S130, carrying out terminal edge carboxylation on the prepared graphene triangle electrode pair to prepare a graphene electrode containing carboxyl functional groups;
And S140, enabling the target compound with the amino terminal and the graphene electrode with the carboxyl functional group at the edge to generate an amide covalent bond connection reaction to form a single-molecule heterojunction, so as to prepare the single-molecule field effect transistor.
3. The method of claim 2, wherein S120 comprises the steps of:
S121, preparing a silicon substrate as a back gate substrate;
s122, preparing a gold mark on the prepared silicon substrate, and preparing the silicon substrate with the gold mark;
S123, selecting a plurality of graphite sheets, arranging the graphite sheets in a row, sequentially adhering the graphite sheets to one end of a transparent adhesive tape, and repeatedly folding the adhesive tape to uniformly distribute the graphite sheets on the adhesive tape;
In order to reduce oxygen dangling bonds on the silicon substrate, enabling the graphene sample to be attached to the silicon substrate, and etching the silicon substrate with the gold mark prepared in the step S122 by using oxygen plasma;
Reversely buckling the surface of the silicon substrate downwards on a tape adhered with graphite, heating the whole silicon substrate on a heating table, then slowly removing the silicon substrate from the tape, removing a graphene sample and adhesive tape residual adhesive on the silicon substrate, and annealing the silicon substrate with the graphene sample in hydrogen to prepare the silicon substrate with graphene;
s124, preparing a graphene electrode with metal electrodes at two ends by using a silicon substrate with graphene, wherein the metal electrodes at two ends of the graphene electrode are a metal source electrode and a metal drain electrode respectively.
4. The preparation method according to claim 2, wherein in S130, the end carboxylated graphene electrode is prepared by oxidizing modification of the carboxyl functional groups at the edges of the graphene electrode by a full dry method of carbon dioxide gas oxidation.
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