CN117263937A - PDI free radical derivative and graphene spin field effect transistor - Google Patents

PDI free radical derivative and graphene spin field effect transistor Download PDF

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Publication number
CN117263937A
CN117263937A CN202311365713.3A CN202311365713A CN117263937A CN 117263937 A CN117263937 A CN 117263937A CN 202311365713 A CN202311365713 A CN 202311365713A CN 117263937 A CN117263937 A CN 117263937A
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graphene
compound
pdi
electrode
radical derivative
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郭雪峰
齐子源
李光武
汪博宇
赵璁
贾传成
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Nankai University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D471/02—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 system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3611—Organic materials containing Nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • 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 a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
    • 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
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Abstract

The invention relates to the technical field of molecular electronic devices, in particular to a PDI free radical derivative and a graphene spin field effect transistor. The PDI radical derivative includes the following structural formula:wherein when R is 2 And R is 3 Is (CH) 2 ) n NH 2 When R is 1 Is that，R 4 Is H orWherein n is 3, 4, 5 or 6; when R is 1 And R is 4 Is (CH) 2 ) n NH 2 When R is 2 Is that，R 3 Is H orWherein n is 3, 4, 5 or 6. The PDI free radical derivative has stable free radicals, so that the PDI free radical derivative has unique conductivity, magnetic property and nonlinear optical property, and can generate stable spin current when being matched with a magnetic electrode and a graphene point electrode pair in a graphene spin field effect transistor, so that the graphene spin field effect transistor has strong stability, high reliability and excellent performance.

Description

PDI free radical derivative and graphene spin field effect transistor
Technical Field
The invention relates to the technical field of molecular electronic devices, in particular to a PDI free radical derivative and a graphene spin field effect transistor.
Background
With the rapid development of information technology, the demands of the society on chip performance are higher and higher, and the importance of miniaturized components is further reflected. While conventional electronic device dimensions have approached physical limits, semiconductor process developments have required exploration of new mechanisms to further advance device miniaturization. The single-molecule electronic device is beneficial to realizing the miniaturization of the device. At present, research on single-molecule electronic devices is mainly focused on spin research of single-molecule electronic devices, while spin research based on single-molecule electronic devices is mainly focused on single-molecule magnets based on magnetic metal complexes, and single-molecule electronic devices obtained based on the above research have poor performance.
Disclosure of Invention
The present invention is directed to solving at least one of the technical problems existing in the related art. Therefore, the invention provides the PDI free radical derivative, which has stable free radicals, so that the PDI free radical derivative has unique conductivity, magnetic property and nonlinear optical property, and can generate stable spin current when being matched with a magnetic electrode and a graphene point electrode pair in the graphene spin field effect transistor, so that the graphene spin field effect transistor has strong stability, high reliability and excellent performance.
In one aspect of the invention, the invention provides a PDI radical derivative comprising the following structural formula:
wherein when R is 2 And R is 3 Is (CH) 2 ) n NH 2 When R is 1 Is that，R 4 Is H or->Wherein n is 3, 4, 5 or 6;
when R is 1 And R is 4 Is (CH) 2 ) n NH 2 When R is 2 Is that，R 3 Is H or->Wherein n is 3, 4, 5 or 6.
Further, the PDI radical derivative includes at least one of structural formulas shown as formula (1) to formula (4):
（1）、
（2）、
(3) And
（4）。
in another aspect of the present invention, there is provided a graphene spin field effect transistor comprising:
A silicon substrate;
the gate dielectric layer is arranged on one surface of the silicon substrate;
the gold electrode and the magnetic electrode are positioned on one side of the gate dielectric layer far away from the silicon substrate, and are oppositely arranged;
the graphene point electrode pair is arranged on the surface, far away from the silicon substrate, of the gate dielectric layer, one electrode of the graphene point electrode pair is electrically connected with the gold electrode, and the other electrode of the graphene point electrode pair is electrically connected with the magnetic electrode;
the graphene dot electrode pair further comprises the PDI free radical derivative, wherein the PDI free radical derivative is connected with two electrodes which are arranged in the graphene dot electrode pair at intervals.
Further, the magnetic electrode includes at least one of iron, cobalt, and nickel;
the gold electrode comprises a chromium layer and a gold layer, wherein the chromium layer is arranged on the surface, far away from the silicon substrate, of the gate dielectric layer, and the gold layer is arranged on the surface, far away from the silicon substrate, of the chromium layer.
Further, the graphene spin field effect transistor further includes: and the protective layer is arranged on one side, far away from the silicon substrate, of the graphene point electrode pair and covers the gold electrode, the magnetic electrode and the graphene point electrode pair.
In another aspect of the present invention, there is provided a method of preparing a graphene spin field effect transistor as described above, the method comprising:
s1, a gate dielectric layer is arranged on one surface of a silicon substrate;
s2, arranging a gold electrode and a magnetic electrode on one side, far away from the silicon substrate, of the gate dielectric layer, and enabling the gold electrode and the magnetic electrode to be arranged oppositely;
s3, arranging a graphene point electrode pair on the surface of the gate dielectric layer, which is far away from the silicon substrate, and enabling one electrode of the graphene point electrode pair to be electrically connected with the gold electrode and the other electrode of the graphene point electrode pair to be electrically connected with the magnetic electrode, so as to obtain a silicon wafer containing the graphene point electrode pair;
and S4, connecting a PDI free radical derivative between two electrodes arranged in the graphene point electrode pair at intervals to obtain the graphene spin field effect transistor.
Further, the preparation method of the PDI free radical derivative comprises the following steps:
1, 8-naphthalimide and 3-bromo-1, 8-naphthalimide are dissolved in diethylene glycol dimethyl ether, and react under the combined catalysis of 2,5 dichloro-cyanobenzene and potassium tert-butoxide at 120-140 ℃ to obtain a first compound;
Dissolving the first compound and 3-bromopropanol in N, N-dimethylformamide, and reacting under the combined catalysis of potassium carbonate and potassium iodide at 110-130 ℃ to obtain a second compound;
dissolving the second compound and 2, 5-tertiary butyl-3-boron dihydroxy-phenol in toluene, and reacting under the combined catalysis of tetra (triphenylphosphine) palladium and sodium carbonate at 110-130 ℃ to obtain a third compound;
dissolving the third compound in tetrahydrofuran, and reacting under the combined catalysis of cesium carbonate, palladium acetate and 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine at the temperature of 80-100 ℃ to obtain a fourth compound;
and dissolving the fourth compound in diethyl ether, and reacting at normal temperature under the combined catalysis of potassium hexacyanoferrate and sodium hydroxide to obtain the PDI free radical derivative.
Further, the preparation method of the PDI free radical derivative comprises the following steps:
dissolving 3-bromo-1, 8-naphthalimide in diethylene glycol dimethyl ether, and reacting under the combined catalysis of 2,5 dichloro-cyanobenzene and potassium tert-butoxide at 120-140 ℃ to obtain a fifth compound;
dissolving the fifth compound and 3-bromopropanol in N, N-dimethylformamide, and reacting under the combined catalysis of potassium carbonate and potassium iodide at 110-130 ℃ to obtain a sixth compound;
Dissolving the sixth compound and 2, 5-tertiary butyl-3-boron dihydroxy-phenol in toluene, and reacting under the combined catalysis of tetra (triphenylphosphine) palladium and sodium carbonate at 110-130 ℃ to obtain a seventh compound;
dissolving the seventh compound in tetrahydrofuran, and reacting under the combined catalysis of cesium carbonate, palladium acetate and 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine at the temperature of 80-100 ℃ to obtain an eighth compound;
and dissolving the eighth compound in diethyl ether, and reacting at normal temperature under the combined catalysis of potassium hexacyanoferrate and sodium hydroxide to obtain the PDI free radical derivative.
Further, the preparation method of the PDI free radical derivative comprises the following steps:
dissolving 5- (3-hydroxypropyl) -1H-benzisoquinoline-1, 3 (2H) -dione in diethylene glycol dimethyl ether, and reacting under the combined catalysis of 2,5 dichloro-cyanobenzene and potassium tert-butoxide at 120-140 ℃ to obtain a ninth compound;
dissolving the ninth compound and the 1, 8-diazacyclo in toluene, cooling the mixture to 0 ℃, then dissolving the mixture with triphenylphosphine and ammonia water in pyridine, and reacting at room temperature to obtain a tenth compound;
dissolving the tenth compound in tetrahydrofuran, and reacting under the catalysis of potassium hydroxide to obtain an eleventh compound;
And dissolving the eleventh compound in diethyl ether, and reacting at normal temperature under the combined catalysis of potassium hexacyanoferrate and sodium hydroxide to obtain the PDI free radical derivative.
Further, step S4 includes:
mixing the silicon wafer containing the graphene dot electrode pairs with a sufficient amount of 1- (3-dimethylaminopropyl) -3-2-ethylcarbodiimide hydrochloride and a PDI free radical derivative to obtain a mixed system;
placing the mixed system in a nitrogen atmosphere, injecting anhydrous pyridine into the mixed system, and standing;
washing and drying the silicon wafer containing the graphene point electrode pairs to obtain the graphene spin field effect transistor;
and/or, the preparation method further comprises:
and arranging a protective layer on one side of the graphene point electrode pair, which is far away from the silicon substrate, so that the gold electrode, the magnetic electrode and the graphene point electrode pair are covered by the protective layer.
The above technical solutions in the embodiments of the present invention have at least one of the following technical effects:
the PDI free radical derivative provided by the invention has stable free radicals, so that the PDI free radical derivative has unique conductivity, magnetic property and nonlinear optical property, the structure of the PDI free radical derivative is easy to regulate and control, the electron spin state is stable, the PDI free radical derivative is more suitable for single-molecule spin control, the spin electron is easy to precisely control by matching with a magnetic electrode and a graphene point electrode pair in a graphene spin field effect transistor, stable spin current can be generated, and the single-molecule spin can be regulated and controlled by matching with a high-kappa solid gate, so that the single-molecule spin current transportation and spin regulation can be realized, and the graphene spin field effect transistor has strong stability, high reliability and excellent performance.
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
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a graphene spin field effect transistor provided by the invention.
Fig. 2 is an I/V graph of a graphene spin field effect transistor obtained in example 1 of the present invention.
Fig. 3 is an I/V graph of another graphene spin field effect transistor obtained in example 1 of the present invention.
Fig. 4 is an I/V graph of another graphene spin field effect transistor obtained in example 1 of the present invention.
Reference numerals:
1. a graphene dot electrode pair; 2. a gold electrode; 3. a magnetic electrode; 4. a silicon substrate; 5. a protective layer; 6. a PDI radical derivative; 7. and a gate dielectric layer.
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 description of the embodiments of the present invention, it should be noted that the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the embodiments of the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the embodiments of the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In describing embodiments of the present invention, it should be noted that, unless explicitly stated and limited otherwise, the terms "coupled," "coupled," and "connected" should be construed broadly, and may be either a fixed connection, a removable connection, or an integral connection, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium. The specific meaning of the above terms in embodiments of the present invention will be understood in detail by those of ordinary skill in the art.
In embodiments of the invention, unless expressly specified and limited otherwise, a first feature "up" or "down" on a second feature may be that the first and second features are in direct contact, or that the first and second features are in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the embodiments of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
In one aspect of the invention, the invention provides a PDI radical derivative comprising the following structural formula:
wherein when R is 2 And R is 3 Is (CH) 2 ) n NH 2 When R is 1 Is that，R 4 Is H or->Wherein n is 3, 4, 5 or 6; when R is 1 And R is 4 Is (CH) 2 ) n NH 2 When R is 2 Is->，R 3 Is H or->Wherein n is 3, 4, 5 or 6.
The radical means an atom, a molecule, and an ion containing unpaired electrons, and is also called a radical. Most of free radicals formed by unpaired electrons have strong electrophilicity, higher energy and strong electron repulsive force, so that the free radicals have high chemical activity and are easy to undergo reactions such as hydrogen abstraction, oxidation, disproportionation, dimerization and the like.
The inventor surprisingly found that in the aspect of molecular materials, single unpaired electrons on free radical molecules can be used as a basic unit with controllable spin, and the number of the free radicals can be effectively controlled through molecular design and external regulation, so that a foundation is provided for accurately controlling spin electrons in a graphene spin field effect transistor.
The inventors have unexpectedly found that the PDI (perylene tetracarboxylic diimide (3,4,9,6-Perylenetetracarboxylic diimide) is simply referred to as perylene diimide) molecule has strong pi-pi conjugation effect, electron affinity comparable to fullerene and strong electron deficiency characteristics, so that the derivative thereof obtains electrons to generate stable free radicals, and the generation of the free radicals is ensured.
The PDI free radical derivative provided by the invention has stable free radicals, so that the PDI free radical derivative has unique conductivity, magnetic property and nonlinear optical property, the structure of the PDI free radical derivative is easy to regulate and control, the electron spin state is stable, the PDI free radical derivative is more suitable for single-molecule spin control, the spin electron is easy to precisely control by matching with a magnetic electrode and a graphene point electrode pair in a graphene spin field effect transistor, stable spin current can be generated, and the single-molecule spin can be regulated and controlled by matching with a high-kappa solid gate, so that the single-molecule spin current transportation and spin regulation can be realized, and the graphene spin field effect transistor has strong stability, high reliability and excellent performance.
In some embodiments of the invention, the PDI radical derivative includes at least one of the structural formulae shown in formulae (1) to (4):
（1）、
（2）、
(3) And
（4）。
in another aspect of the present invention, there is provided a graphene spin field effect transistor, referring to fig. 1, comprising: a silicon substrate 4; a gate dielectric layer 7, wherein the gate dielectric layer 7 is arranged on one surface of the silicon substrate 4; the gold electrode 2 and the magnetic electrode 3 are positioned on one side of the gate dielectric layer 7 away from the silicon substrate 4, and the gold electrode 2 and the magnetic electrode 3 are oppositely arranged; a pair of graphene dot electrodes 1, wherein the pair of graphene dot electrodes 1 is arranged on the surface of the gate dielectric layer 7, which is far away from the silicon substrate 4, one electrode of the pair of graphene dot electrodes 1 is electrically connected with the gold electrode 2, and the other electrode of the pair of graphene dot electrodes 1 is electrically connected with the magnetic electrode 3; the graphene dot electrode pair 1 further comprises a PDI free radical derivative 6 as described above, and the PDI free radical derivative 6 is connected with two electrodes arranged in the middle of the graphene dot electrode pair 1.
It is understood that the gold electrode and the magnetic electrode may be directly disposed on the surface of the gate dielectric layer, or may be disposed on the surface of the graphene dot electrode pair. The magnetic electrode filters the spin state in order to induce spin current so that a fixed spin type is obtained.
In the graphene spin field effect transistor, two ends are provided with-NH 2 The PDI free radical derivative is used as a single molecule which is bridged, and is connected with the end of a graphene point electrode with-COOH to form an amide covalent bond, so that the graphene spin field effect transistor based on the PDI free radical derivative is constructed, technical support is provided for researching molecular spin state regulation and spin transport on a single molecular scale, and a foundation is laid for development of the quantum information field. In the graphene spin field effect transistor, stable spin current is input based on the matching of a magnetic electrode structure and a graphene point electrode pair, and the spin state of a single electron and spin coupling of multiple electrons can be controlled through accurate injection of external field regulation and transportation spin electrons, so that single-molecule spin current transportation and spin regulation are realized.
In some embodiments of the invention, the magnetic electrode comprises at least one of iron, cobalt, and nickel; the gold electrode comprises a chromium layer and a gold layer, wherein the chromium layer is arranged on the surface, far away from the silicon substrate, of the gate dielectric layer, and the gold layer is arranged on the surface, far away from the silicon substrate, of the chromium layer.
In some embodiments of the present invention, referring to fig. 1, the graphene spin field effect transistor further includes: and the protective layer 5 is arranged on one side of the graphene point electrode pair 1, which is far away from the silicon substrate 4, and covers the gold electrode 2, the magnetic electrode 3 and the graphene point electrode pair 1. In some embodiments of the present invention, the material of the protective layer includes hexagonal boron nitride (h-BN), and the hexagonal boron nitride protective layer is used to encapsulate the graphene spin field effect transistor, so as to improve the stability of the device.
In another aspect of the present invention, there is provided a method of preparing a graphene spin field effect transistor as described above, the method comprising:
s1, a gate dielectric layer is arranged on one surface of a silicon substrate.
In some embodiments of the present invention, the specific step of disposing a gate dielectric layer on one surface of a silicon substrate includes:
and S11, photoetching a grid electrode on a pure silicon wafer substrate with 300-400 nm silicon oxide covered on the surface, evaporating metal, and removing photoresist by using acetone to obtain a negative film. The photoetching grid electrode is used for needle-down test and photoetching calibration in subsequent experiments. The vapor deposition metal is prepared by vapor deposition of 8-10 nm chromium and then 60-80 nm gold by thermal vapor deposition.
And S12, continuing to photoetching the grid on the negative film to obtain a bottom grid connected with the evaporated metal.
And S13, plating an aluminum film on the surface of the bottom gate, and removing the glue by using acetone to obtain the aluminum oxide dielectric layer. The aluminum film is prepared by a magnetron sputtering method, and the thickness of the film coating is 30-40 nm. The alumina dielectric layer is obtained by naturally oxidizing an aluminum film after removing the colloid by acetone.
S14, plating a hafnium oxide film on the surface of the aluminum oxide dielectric layer to obtain a final solid gate dielectric layer. The hafnium oxide film adopts an atomic beam deposition method, and the thickness of the film coating is 3-10 nm.
In some embodiments of the present invention, before disposing the gold electrode and the magnetic electrode, disposing a graphene layer on a surface of the gate dielectric layer away from the silicon substrate, the steps including:
s15, preparing single-layer graphene on the copper foil by using a chemical vapor deposition method.
S16, spin-coating methyl methacrylate (950 PMMA) on the single-layer graphene to obtain the PMMA-graphene-copper foil structure.
S17, cutting and placing the PMMA-graphene-copper foil structure in FeCl 3 And (2) dissolving copper foil in the solution, soaking the copper foil in hydrochloric acid solution, alkali solution and pure water, transferring the copper foil to the surface of the gate dielectric layer obtained in the step (S1), naturally air-drying the copper foil, and removing the glue. Wherein, the glue removal can adopt two methods: (1) Heating the silicon wafer subjected to graphene transfer by using an acetone solution at 120 ℃ for 8 minutes to remove the colloid; (2) And (3) placing the silicon wafer in a heating furnace, and heating at 400-500 ℃ for 1-2 minutes to remove the glue.
S2, arranging a gold electrode and a magnetic electrode on one side, far away from the silicon substrate, of the gate dielectric layer, and enabling the gold electrode and the magnetic electrode to be arranged oppositely.
In some embodiments of the present invention, the specific steps of disposing a gold electrode and a magnetic electrode on a side of the gate dielectric layer away from the silicon substrate include:
S21, gluing a graphene film layer, photoetching a strip, performing oxygen plasma etching, and removing the glue by using acetone to obtain a graphene strip; the photoetching uses an ultraviolet photoetching machine, and the length of graphene strips obtained by photoetching is 200 mu m, and the width of the graphene strips is 40 mu m. And (3) protecting the graphene strips obtained by photoetching by using photoresist, exposing the rest graphene, and removing the graphene outside the strips by using oxygen plasma etching to obtain the graphene strips only protected by using the intermediate photoresist.
S22, gluing the surface of the graphene strip, photoetching an electrode, plating a magnetic material on one side electrode, and removing the glue by using acetone to obtain the silicon wafer containing the magnetic electrode. Wherein, the magnetic material adopts magnetron sputtering coating, and the thickness is 70 nm.
And S23, gluing and photoetching the electrode on the silicon wafer containing the magnetic electrode, steaming chromium and gold on the other side, and removing the glue to obtain the graphene array electrode. Wherein, 8 nm chromium is firstly evaporated by a thermal evaporation method, and then 80 nm gold is evaporated. The middle part structure of the magnetic electrode and the gold electrode is called a graphene channel and is used for constructing a graphene point electrode.
S24, testing the conductivity of the graphene array electrode under the voltage of 50 mV, screening out the silicon wafer with the conductivity of 10 mu A level, and continuing the subsequent experiment.
And S3, arranging a graphene point electrode pair on the surface of the gate dielectric layer, which is far away from the silicon substrate, and enabling one electrode of the graphene point electrode pair to be electrically connected with the gold electrode and the other electrode of the graphene point electrode pair to be electrically connected with the magnetic electrode, so as to obtain the silicon wafer containing the graphene point electrode pair.
In some embodiments of the present invention, the specific operation steps of disposing the graphene point electrode pair on the surface of the gate dielectric layer away from the silicon substrate include:
and S31, etching and developing the graphene array electrode by using an electron beam exposure machine to obtain the graphene array electrode with the dotted line between the electrode pairs. Wherein, the broken line etched by the electron beam exposure machine is positioned between each pair of magnetic electrodes and gold electrodes, the total length is 60 mu m, the length of each broken line segment is 150 nm, and the interval between the broken lines is 40 nm. The developing solution used for the development was methyl isobutyl ketone (MIBK) diluted with isopropyl alcohol, MIBK: isopropyl alcohol=1:3, and the fixing solution was isopropyl alcohol.
S32, carrying out oxygen plasma etching on the graphene array electrode with the dotted line, testing the current between the electrode pairs by using the probe table and the source meter, and obtaining graphene point electrode pairs after a plurality of times of circulation of the current, wherein a gap exists between two electrodes of each pair of graphene point electrodes.
The input voltage of the source meter is 50 mV, and the graphene point electrode pairs can be considered to be obtained when the current between every ten pairs of electrodes is several mu A magnitude.
And S4, connecting a PDI free radical derivative between two electrodes arranged in the graphene point electrode pair at intervals to obtain the graphene spin field effect transistor.
In some embodiments of the invention, step S4 comprises: mixing the silicon wafer containing the graphene dot electrode pairs with a sufficient amount of 1- (3-dimethylaminopropyl) -3-2-ethylcarbodiimide hydrochloride and a PDI free radical derivative to obtain a mixed system; placing the mixed system in a nitrogen atmosphere, injecting anhydrous pyridine into the mixed system, and standing; and cleaning and drying the silicon wafer containing the graphene point electrode pair to obtain the graphene spin field effect transistor.
In some embodiments of the invention, step S4 comprises:
s41, placing the silicon wafer containing the graphene dot electrode pair into a two-neck flask, and adding enough 1- (3-dimethylaminopropyl) -3-2-ethylcarbodiimide hydrochloride and PDI free radical derivatives into the flask.
Wherein, the two-mouth flask, all experimental devices and experimental materials are in anhydrous state to ensure the-NH at two ends of the molecule 2 The method can smoothly bridge amide covalent bonds formed by the graphene dot electrode pair and the terminal-COOH, so that the graphene spin field effect transistor is obtained, and the sign of successful bridging is that under the condition of constant bias voltage, the current changes along with the change of the gate voltage, so that the regulation and control of the gate voltage on the device are realized.
In some embodiments of the present invention, 1- (3-dimethylaminopropyl) -3-2-ethylcarbodiimide hydrochloride is used as the activator at a concentration of 3X 10 -3 mol/L。
S42, sealing the two-neck flask, and repeatedly introducing and extracting nitrogen three times to enable the two-neck flask to be in a nitrogen atmosphere.
S43, 10ml of anhydrous pyridine is extracted by a syringe and a long needle and injected into the two-mouth flask.
And S44, standing the system obtained in the step S43 for 48 hours, taking out the silicon wafer, flushing with acetone and ultrapure water, and drying the surface to obtain the graphene spin field effect transistor.
The method comprises the steps of regulating the position distribution of spin electrons on a PDI free radical derivative structure in a given grid voltage electric field, regulating the coupling between the spin electrons in molecules and spin electrons at the edge of an electrode through monitoring the electrical characteristics of the device in real time, observing the change of output conductance of a molecular device with time under different grid voltages, testing the differential conductance spectrum of the device in a bias range of +/-10 mV by using a lock-in amplifier based on a near-rattan effect and a Zeeman effect in a low-temperature environment of 50mK-2K, and judging the spin state of the free radical molecules and the spin energy regulation condition of the free radicals in the device through a near-rattan characteristic signal.
In some embodiments of the present invention, the method for preparing a graphene spin field effect transistor further comprises: and arranging a protective layer on one side of the graphene point electrode pair, which is far away from the silicon substrate, so that the gold electrode, the magnetic electrode and the graphene point electrode pair are covered by the protective layer.
In some specific embodiments of the invention, a layer of h-BN protective layer of 1-20 nm is plated on the surfaces of the gold electrode, the magnetic electrode and the graphene dot electrode pair.
In some embodiments of the invention, the method for preparing the PDI radical derivative comprises: 1, 8-naphthalimide and 3-bromo-1, 8-naphthalimide are dissolved in diethylene glycol dimethyl ether, and react under the combined catalysis of 2,5 dichloro-cyanobenzene and potassium tert-butoxide at 120-140 ℃ to obtain a first compound; dissolving the first compound and 3-bromopropanol in N, N-dimethylformamide, and reacting under the combined catalysis of potassium carbonate and potassium iodide at 110-130 ℃ to obtain a second compound; dissolving the second compound and 2, 5-tertiary butyl-3-boron dihydroxy-phenol in toluene, and reacting under the combined catalysis of tetra (triphenylphosphine) palladium and sodium carbonate at 110-130 ℃ to obtain a third compound; dissolving the third compound in tetrahydrofuran, and reacting under the combined catalysis of cesium carbonate, palladium acetate and 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine at the temperature of 80-100 ℃ to obtain a fourth compound; dissolving the fourth compound in diethyl ether, and reacting at normal temperature under the combined catalysis of potassium hexacyanoferrate and sodium hydroxide to obtain the PDI free radical derivative, wherein the specific synthesis flow is as follows:
/>
。
In other embodiments of the present invention, the method for preparing a PDI radical derivative comprises: dissolving 3-bromo-1, 8-naphthalimide in diethylene glycol dimethyl ether, and reacting under the combined catalysis of 2,5 dichloro-cyanobenzene and potassium tert-butoxide at 120-140 ℃ to obtain a fifth compound; dissolving the fifth compound and 3-bromopropanol in N, N-dimethylformamide, and reacting under the combined catalysis of potassium carbonate and potassium iodide at 110-130 ℃ to obtain a sixth compound; dissolving the sixth compound and 2, 5-tertiary butyl-3-boron dihydroxy-phenol in toluene, and reacting under the combined catalysis of tetra (triphenylphosphine) palladium and sodium carbonate at 110-130 ℃ to obtain a seventh compound; dissolving the seventh compound in tetrahydrofuran, and reacting under the combined catalysis of cesium carbonate, palladium acetate and 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine at the temperature of 80-100 ℃ to obtain an eighth compound; the eighth compound is dissolved in diethyl ether and reacts at normal temperature under the combined catalysis of potassium hexacyanoferrate and sodium hydroxide, and the specific synthesis flow of the PDI free radical derivative is shown as follows:
/>
。
In other embodiments of the present invention, the method for preparing a PDI radical derivative comprises: dissolving 5- (3-hydroxypropyl) -1H-benzisoquinoline-1, 3 (2H) -dione in diethylene glycol dimethyl ether, and reacting under the combined catalysis of 2,5 dichloro-cyanobenzene and potassium tert-butoxide at 120-140 ℃ to obtain a ninth compound; dissolving the ninth compound and the 1, 8-diazacyclo in toluene, cooling the mixture to 0 ℃, then dissolving the mixture with triphenylphosphine and ammonia water in pyridine, and reacting at room temperature to obtain a tenth compound; dissolving the tenth compound in tetrahydrofuran, and reacting under the catalysis of potassium hydroxide to obtain an eleventh compound; and dissolving the eleventh compound in diethyl ether, and reacting at normal temperature under the combined catalysis of potassium hexacyanoferrate and sodium hydroxide to obtain the PDI free radical derivative.
It should be noted that, the amounts of 5- (3-hydroxypropyl) -1H-benzisoquinoline-1, 3 (2H) -dione are different, the structural formulas of the ninth compounds obtained are different, and further, the structural formulas of the tenth to eleventh compounds and even the PDI radical derivatives are also different, and when the amounts of 5- (3-hydroxypropyl) -1H-benzisoquinoline-1, 3 (2H) -dione are small, the procedure for synthesizing the PDI radical derivatives is as follows:
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。
When 5- (3-hydroxypropyl) -1H-benzisoquinoline-1, 3 (2H) -dione is used in a large amount, the procedure for synthesizing the PDI radical derivative is shown below:
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the invention will be described in detail with reference to specific examples.
Examples
Example 1
The preparation method of the PDI free radical derivative comprises the following steps:
1. 1 g (5.07 mmol) of 1, 8-naphthalenedicarboximide, 1.2 g (5.07 mmol) of 3-bromo-1, 8-naphthalenedicarboximide, 0.112 g (10%) of 2,5 dichloro-cyanobenzene, 0.112 g (10%) of potassium tert-butoxide were taken and dissolved in 20 ml diethylene glycol dimethyl ether, heated to 130℃and stirred for reaction for 12 hours. After the reaction was completed, the liquid phase mixture was extracted with dichloromethane and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 1 in 43% yield. ESI-TOF: C 24 H 9 BrN 2 O 4 , Mw=467.97. 1 H NMR (800 MHz, DMSO-d6) δ 8.57 (s, 1H), 8.49 – 8.45 (m, 3H), 8.11 (dd, J = 8.5, 7.9 Hz, 2H), 8.06 (d, J = 8.4 Hz, 1H).
1 g (2.14 mmol) of Compound 1 was taken and reacted with 0.301 g (2.2 mmol) of 3-bromopropanol, 0.036 g (10%) of potassium carbonate, 0.042 g (10%) of potassium iodide, dissolved in 15 ml of DMF, heated to 120℃and stirred for 20 hours. After the reaction was completed, the liquid phase mixture was extracted with dichloromethane and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 2 in 70% yield. ESI-TOF: C 32 H 25 BrN 2 O 6 , Mw=613.46. 1 H NMR (800 MHz, DMSO-d6) δ 8.55 (dd, J = 8.6, 5.2 Hz, 2H), 8.49 (d, J = 8.6 Hz, 1H), 8.18 (s, 1H), 8.14 (d, J = 8.6 Hz, 1H), 8.10 (d, J = 8.6 Hz, 1H), 8.05 (d, J = 8.6 Hz, 1H), 4.21 (d, J = 11.7 Hz, 1H), 3.58 (td, J = 5.8, 1.9 Hz, 4H), 3.54 (q, J = 5.8 Hz, 4H), 1.70 (ttd, J = 8.3, 5.7, 0.7 Hz, 4H), 1.58 (ttd, J = 8.4, 5.8, 0.8 Hz, 4H).
1. 1g (1.6 mmol) of Compound 2,0.40 g (1.6 mmol) of 2, 5-tert-butyl-3-borodihydroxy-phenol, 0.012 g (2%) of tetrakis (triphenylphosphine) palladium, 0.036g (10%) of sodium carbonate were taken, dissolved in 20 ml toluene, heated to 120℃and reacted for 24 hours with stirring. After the reaction, the liquid phase mixture was extracted with dichloromethane and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 3 in 90% yield. ESI-TOF: C 46 H 46 N 2 O 7 , Mw=738.33. 1 H NMR (800 MHz, DMSO-d6) δ 8.56 (dd, J = 8.6, 7.9 Hz, 1H), 8.47 (d, J = 8.6 Hz, 1H), 8.20 (s, 1H), 8.16 – 8.07 (m, 1H), 7.37 (s, 1H), 6.84 (s, 1H), 4.21 (t, J = 5.9 Hz, 1H), 3.56 (dt, J = 28.2, 5.8 Hz, 4H), 1.70 (ttd, J = 8.3, 5.8, 0.7 Hz, 2H), 1.58 (ttd, J = 8.5, 5.9, 0.8 Hz, 2H), 1.44 (s, 9H).
1g (1.4 mmol) of Compound 3,0.025 g (10%) of cesium carbonate, 0.036g (4%) of palladium acetate, 0.051 g (6%) of 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine were taken, dissolved in 10 ml of tetrahydrofuran and heated to 9Reaction 12 h was stirred at 0 ℃. After the reaction was completed, the liquid phase mixture was extracted with methylene chloride and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 4 in 82% yield. ESI-TOF: C 46 H 48 N 4 O 5 , Mw=736.36. 1 H NMR (800 MHz, DMSO-d6) δ 8.56 (dd, J = 8.6, 7.9 Hz, 1H), 8.47 (d, J = 8.6 Hz, 1H), 8.20 (s, 1H), 8.16 – 8.07 (m, 1H), 7.37 (s, 1H), 6.84 (s, 1H), 3.54 (dt, J = 12.4, 6.2 Hz, 1H), 3.51 – 3.46 (m, 1H), 2.83 (tt, J = 6.5, 5.2 Hz, 2H), 2.09 (t, J = 6.5 Hz, 2H), 1.71 – 1.65 (m, 2H), 1.58 (ttd, J = 7.8, 5.2, 0.8 Hz, 2H), 1.44 (s, 9H)。
1. 1g (1.36 mmol) of Compound 4,0.078 g (10%) of potassium hexacyanoferrate, 0.012 g (20%) of sodium hydroxide were taken and dissolved in 10 ml of diethyl ether, and allowed to stand at room temperature for 2 hours, after the reaction was completed, the liquid phase mixture was extracted with methylene chloride and washed three times with a saturated sodium chloride solution, and the organic phase was dried to give a PDI free radical derivative in 87% yield.
3 graphene spin field effect transistors are prepared by using the PDI free radical derivative of the embodiment, and performance test results of the 3 graphene spin field effect transistors are shown in fig. 2 to 4. It should be noted that, as shown in fig. 2 to 4, the performance test results of the 3 graphene spin field effect transistors obtained in this embodiment are not exactly the same, but are not much different.
Example 2
The preparation method of the PDI free radical derivative comprises the following steps:
1.2. 1.2 g (5.07 mmol) of 3-bromo-1, 8-naphthalimide, 0.056 g (10%) of 2,5 dichloro-cyanobenzene and 0.055 g (10%) of potassium tert-butoxide were taken and dissolved in 20 ml of diethylene glycol dimethyl ether, heated to 130℃and stirred for reaction for 12 hours. After the reaction was completed, the liquid phase mixture was extracted with methylene chloride and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 5 in 91% yield. ESI-TOF: C 24 H 8 Br 2 N 2 O 4 , Mw=548.15. 1 H NMR (800 MHz, DMSO-d6) δ 8.58 (s, 2H), 8.46 (d, J = 8.4 Hz, 2H), 8.07 (d, J = 8.4 Hz, 1H), 8.03 (d, J = 8.5 Hz, 1H)。
1 g (1.82 mmol) of Compound 5 was taken and reacted with 0.265 g (1.90 mmol) of 3-bromopropanol, 0.032 g (10%) of potassium carbonate, 0.038 g (10%) of potassium iodide, dissolved in 15 ml of DMF, heated to 120℃and stirred for 20 hours. After the reaction was completed, the liquid phase mixture was extracted with dichloromethane and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 6 in 65% yield. ESI-TOF: C 32 H 24 Br 2 N 2 O 6 , Mw=692.36. 1 H NMR (800 MHz, DMSO-d6) δ 8.49 (d, J = 8.6 Hz, 1H), 8.18 (s, 1H), 8.07 (d, J = 8.6 Hz, 1H), 8.01 (d, J = 8.6 Hz, 1H), 4.21 (t, J = 5.9 Hz, 1H), 3.56 (dt, J = 26.5, 5.8 Hz, 4H), 1.70 (ttd, J = 8.3, 5.8, 0.7 Hz, 2H), 1.58 (ttd, J = 8.4, 5.8, 0.7 Hz, 2H)。
1. 1g (1.45 mmol) of Compound 6,0.36 g (1.45 mmol) of 2, 5-tert-butyl-3-borodihydroxy-phenol, 0.012 g (2%) of tetrakis (triphenylphosphine) palladium, 0.036 g (mmol) of sodium carbonate were taken, dissolved in 20 ml toluene, heated to 120℃and reacted for 24 hours with stirring. After the reaction was completed, the liquid phase mixture was extracted with methylene chloride and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 7 in 88% yield. ESI-TOF: C 60 H 66 N 2 O 8 , Mw=942.48. 1 H NMR (800 MHz, DMSO-d6) δ 8.49 (d, J = 8.6 Hz, 1H), 8.05 (dd, J = 25.4, 8.6 Hz, 0H), 8.01 (s, 1H), 7.37 (s, 1H), 6.84 (s, 1H), 3.58 (t, J = 5.8 Hz, 1H), 3.54 (q, J = 5.8 Hz, 1H), 1.70 (ttd, J = 8.4, 5.8, 0.7 Hz, 1H), 1.58 (ttd, J = 8.4, 5.8, 0.7 Hz, 1H), 1.44 (s, 9H)。
1g (1.06 mmol) of Compound 7,0.015 g (10%) of cesium carbonate, 0.031g (4%) of palladium acetate, 0.034 g (6%) of 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine were taken and dissolved in 10 ml of tetrahydrofuran, heated to 90℃and stirred for reaction 12 h. After the reaction, the liquid phase mixture was extracted with methylene chloride and dissolved with saturated sodium chlorideThe solution was washed three times, the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 8 in 84% yield. ESI-TOF: C 60 H 68 N 4 O 6 , Mw=941.23. 1 H NMR (800 MHz, DMSO-d6) δ 8.49 (d, J = 8.6 Hz, 1H), 8.05 (dd, J = 25.4, 8.6 Hz, 1H), 8.01 (s, 1H), 7.37 (s, 2H), 6.84 (s, 1H), 3.54 (dt, J = 12.4, 6.2 Hz, 1H), 3.51 – 3.47 (m, 1H), 2.83 (tt, J = 6.5, 5.2 Hz, 2H), 2.09 (t, J = 6.5 Hz, 2H), 1.71 – 1.65 (m, 2H), 1.58 (ttd, J = 7.8, 5.2, 0.8 Hz, 2H), 1.44 (s, 18H)。
1g (1.05 mmol) of compound 8,0.056 g (10%) of potassium hexacyanoferrate, 0.010 g (20%) of sodium hydroxide were taken and dissolved in 10 ml of diethyl ether, and left standing at room temperature for 2 hours, after the reaction was completed, the liquid phase mixture was extracted with methylene chloride and washed three times with saturated sodium chloride solution, and the organic phase was dried to give a PDI radical derivative in 89% yield.
Example 3
The preparation method of the PDI free radical derivative comprises the following steps:
1.2. 1.2 g (4.7 mmol) of 5- (3-hydroxypropyl) -1H-benzisoquinoline-1, 3 (2H) -dione, 0.056 g (10%) of 2,5 dichloro-cyanobenzene, 0.055 g (10%) of potassium tert-butoxide was taken and dissolved in 20 ml diethylene glycol dimethyl ether, heated to 130℃and reacted with stirring for 12 hours. After the reaction was completed, the liquid phase mixture was extracted with methylene chloride and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 9 in 86% yield. ESI-TOF: C 30 H 22 N 2 O 6 , Mw=506.15. 1 H NMR (800 MHz, DMSO-d6) δ 8.44 (d, J = 8.5 Hz, 2H), 8.12 (s, 2H), 8.07 (dd, J = 9.5, 8.4 Hz, 2H), 4.22 (d, J = 11.3 Hz, 1H), 3.53 (q, J = 5.8 Hz, 4H), 2.82 (t, J = 8.2 Hz, 4H), 1.82 (tt, J = 8.2, 5.9 Hz, 4H)。
1 g (1.98 mmol) of Compound 9, together with 0.036 g (10%) of 1, 8-diaza-ring, was taken and dissolved in 20 ml toluene and cooled to 0deg.C. Then, 0.057g (3%) of triphenylphosphine and 0.033g (4.78 mmol) of aqueous ammonia were dissolved in 15ml of pyridine and reacted at room temperature. After the reaction, dichloromethane was usedThe liquid phase mixture was extracted and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 10 in 70% yield. ESI-TOF: C 30 H 24 N 4 O 4 , Mw=504.18. 1 H NMR (800 MHz, DMSO-d6) δ 8.44 (d, J = 8.5 Hz, 1H), 8.12 (s, 1H), 8.07 (dd, J = 9.5, 8.5 Hz, 1H), 2.88 (d, J = 15.2 Hz, 1H), 2.82 – 2.77 (m, 2H), 1.88 – 1.82 (m, 3H), 1.80 (q, J = 6.4 Hz, 1H)。
1. 1 g (1.98 mmol) of Compound 10 was taken and dissolved in 10 ml tetrahydrofuran with 0.301 g (1.06 mmol) of 4-bromo-2, 6-di-tert-butylphenol, 0.036 g (10%) of potassium hydroxide, and refluxed. After the reaction was completed, the liquid phase mixture was extracted with dichloromethane and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 11 in 34% yield. ESI-TOF: C 44 H 44 N 4 O 5 , Mw=708.33. 1 H NMR (800 MHz, DMSO-d6) δ 8.46 (dd, J = 26.1, 8.5 Hz, 1H), 8.15 (s, 1H), 8.12 (s, 1H), 8.08 (dd, J = 8.5, 0.8 Hz, 1H), 7.78 (s, 1H), 7.19 (s, 1H), 2.88 (t, J = 7.6 Hz, 2H), 2.82 – 2.77 (m, 1H), 1.88 – 1.82 (m, 3H), 1.80 (q, J = 6.4 Hz, 1H), 1.41 (s, 9H)。
1 g (1.05 mmol) of compound 11,0.056 g (10%) of potassium hexacyanoferrate, 0.010 g (20%) of sodium hydroxide were taken and dissolved in 10 ml of diethyl ether, and left standing at room temperature for 2 hours, after the reaction was completed, the liquid phase mixture was extracted with methylene chloride and washed three times with saturated sodium chloride solution, and the organic phase was taken to dryness to obtain a PDI radical derivative in 93% yield.
Example 4
The preparation method of the PDI free radical derivative comprises the following steps:
1.2. 1.2 g (5.07 mmol) of 5- (3-hydroxypropyl) -1H-benzisoquinoline-1, 3 (2H) -dione, 0.056 g (10%) of 2,5 dichloro-cyanobenzene, 0.055 g (10%) of potassium tert-butoxide was taken and dissolved in 20 ml diethylene glycol dimethyl ether, heated to 130℃and reacted with stirring for 12 hours. After the reaction, the liquid phase mixture was extracted with methylene chloride and washed three times with saturated sodium chloride solution to obtain an organic phaseDrying and column chromatography using ethyl acetate and petroleum ether gave compound 12 in 91% yield. ESI-TOF: C 30 H 22 N 2 O 6 , Mw=506.15. 1 H NMR (800 MHz, DMSO-d6) δ 8.44 (d, J = 8.5 Hz, 2H), 8.12 (s, 2H), 8.07 (dd, J = 9.5, 8.4 Hz, 2H), 4.22 (d, J = 11.3 Hz, 1H), 3.53 (q, J = 5.8 Hz, 4H), 2.82 (t, J = 8.2 Hz, 4H), 1.82 (tt, J = 8.2, 5.9 Hz, 4H)。
1 g (1.98 mmol) of Compound 12, together with 0.036 g (10%) of 1, 8-diaza-ring, was taken and dissolved in 20 ml toluene and cooled to 0deg.C. Then, 0.057g (3%) of triphenylphosphine, 0.033g (4.78 mmol) of ammonia monohydrate, dissolved in 15ml of pyridine, and reacted at room temperature. After the reaction was completed, the liquid phase mixture was extracted with methylene chloride and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 13 in 70% yield. ESI-TOF: C 30 H 24 N 4 O 4 , Mw=504.18. 1 H NMR (800 MHz, DMSO-d6) δ 8.44 (d, J = 8.5 Hz, 1H), 8.12 (s, 1H), 8.07 (dd, J = 9.5, 8.5 Hz, 1H), 2.88 (d, J = 15.2 Hz, 1H), 2.82 – 2.77 (m, 2H), 1.88 – 1.82 (m, 3H), 1.80 (q, J = 6.4 Hz, 1H)。
1. 1 g (1.98 mmol) of Compound 13 was taken and dissolved in 10 ml tetrahydrofuran with 0.301 g (1.06 mmol) of 4-bromo-2, 6-di-tert-butylphenol, 0.036 g (10%) of potassium hydroxide, and refluxed. After the reaction was completed, the liquid phase mixture was extracted with methylene chloride and washed three times with saturated sodium chloride solution, and the organic phase was dried and separated by column chromatography using ethyl acetate and petroleum ether to give compound 14 in 37% yield. ESI-TOF: C 58 H 64 N 4 O 6 , Mw=912.48. 1 H NMR (800 MHz, DMSO-d6) δ 8.46 (dd, J = 26.1, 8.5 Hz, 1H), 8.15 (s, 1H), 8.12 (s, 1H), 8.08 (dd, J = 8.5, 0.8 Hz, 1H), 7.78 (s, 1H), 7.19 (s, 1H), 2.88 (t, J = 7.6 Hz, 2H), 2.82 – 2.77 (m, 1H), 1.88 – 1.82 (m, 3H), 1.80 (q, J = 6.4 Hz, 1H), 1.41 (s, 9H)。
1 g (1.05 mmol) of Compound 14,0.056 g (10%) of potassium hexacyanoferrate, 0.010 g (20%) of sodium hydroxide were taken and dissolved in 10 ml of diethyl ether, and left standing at room temperature for 2 hours, after the reaction was completed, the liquid phase mixture was extracted with methylene chloride and washed three times with saturated sodium chloride solution, and the organic phase was dried to give a PDI radical derivative in 91% yield.
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 (10)

1. A PDI radical derivative, wherein the PDI radical derivative comprises the following structural formula:
wherein when R is 2 And R is 3 Is (CH) 2 ) n NH 2 When R is 1 Is that，R 4 Is H or->Wherein n is 3, 4, 5 or 6;
when R is 1 And R is 4 Is (CH) 2 ) n NH 2 When R is 2 Is that，R 3 Is H or->Wherein n is 3, 4, 5 or 6.
2. The PDI radical derivative according to claim 1, wherein the PDI radical derivative comprises at least one of structural formulae shown as formula (1) to formula (4):
（1）、
（2）、
(3) And->（4）。
3. A graphene spin field effect transistor, comprising:
a silicon substrate;
the gate dielectric layer is arranged on one surface of the silicon substrate;
a graphene dot electrode pair, wherein the graphene dot electrode pair is arranged on the surface of the gate dielectric layer far away from the silicon substrate,
the gold electrode and the magnetic electrode are positioned on one side of the gate dielectric layer far away from the silicon substrate, and are oppositely arranged;
one electrode of the graphene point electrode pair is electrically connected with the gold electrode, and the other electrode of the graphene point electrode pair is electrically connected with the magnetic electrode;
The method further comprises the step of connecting the PDI free radical derivative as claimed in claim 1 or 2 with two electrodes arranged in the graphene dot electrode pair at intervals.
4. The graphene spin field effect transistor according to claim 3, wherein the magnetic electrode comprises at least one of iron, cobalt and nickel;
the gold electrode comprises a chromium layer and a gold layer, wherein the chromium layer is arranged on the surface, far away from the silicon substrate, of the gate dielectric layer, and the gold layer is arranged on the surface, far away from the silicon substrate, of the chromium layer.
5. The graphene spin field effect transistor according to claim 4, further comprising: and the protective layer is arranged on one side, far away from the silicon substrate, of the graphene point electrode pair and covers the gold electrode, the magnetic electrode and the graphene point electrode pair.
6. A method for manufacturing a graphene spin field effect transistor according to any one of claims 3 to 5, comprising:
s1, a gate dielectric layer is arranged on one surface of a silicon substrate;
s2, arranging a gold electrode and a magnetic electrode on one side, far away from the silicon substrate, of the gate dielectric layer, and enabling the gold electrode and the magnetic electrode to be arranged oppositely;
S3, arranging a graphene point electrode pair on the surface of the gate dielectric layer, which is far away from the silicon substrate, and enabling one electrode of the graphene point electrode pair to be electrically connected with the gold electrode and the other electrode of the graphene point electrode pair to be electrically connected with the magnetic electrode, so as to obtain a silicon wafer containing the graphene point electrode pair;
and S4, connecting a PDI free radical derivative between two electrodes arranged in the graphene point electrode pair at intervals to obtain the graphene spin field effect transistor.
7. The method for preparing a graphene spin field effect transistor according to claim 6, wherein the method for preparing a PDI radical derivative comprises:
1, 8-naphthalimide and 3-bromo-1, 8-naphthalimide are dissolved in diethylene glycol dimethyl ether, and react under the combined catalysis of 2,5 dichloro-cyanobenzene and potassium tert-butoxide at 120-140 ℃ to obtain a first compound;
dissolving the first compound and 3-bromopropanol in N, N-dimethylformamide, and reacting under the combined catalysis of potassium carbonate and potassium iodide at 110-130 ℃ to obtain a second compound;
dissolving the second compound and 2, 5-tertiary butyl-3-boron dihydroxy-phenol in toluene, and reacting under the combined catalysis of tetra (triphenylphosphine) palladium and sodium carbonate at 110-130 ℃ to obtain a third compound;
Dissolving the third compound in tetrahydrofuran, and reacting under the combined catalysis of cesium carbonate, palladium acetate and 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine at the temperature of 80-100 ℃ to obtain a fourth compound;
and dissolving the fourth compound in diethyl ether, and reacting at normal temperature under the combined catalysis of potassium hexacyanoferrate and sodium hydroxide to obtain the PDI free radical derivative.
8. The method for preparing a graphene spin field effect transistor according to claim 6, wherein the method for preparing a PDI radical derivative comprises:
dissolving 3-bromo-1, 8-naphthalimide in diethylene glycol dimethyl ether, and reacting under the combined catalysis of 2,5 dichloro-cyanobenzene and potassium tert-butoxide at 120-140 ℃ to obtain a fifth compound;
dissolving the fifth compound and 3-bromopropanol in N, N-dimethylformamide, and reacting under the combined catalysis of potassium carbonate and potassium iodide at 110-130 ℃ to obtain a sixth compound;
dissolving the sixth compound and 2, 5-tertiary butyl-3-boron dihydroxy-phenol in toluene, and reacting under the combined catalysis of tetra (triphenylphosphine) palladium and sodium carbonate at 110-130 ℃ to obtain a seventh compound;
Dissolving the seventh compound in tetrahydrofuran, and reacting under the combined catalysis of cesium carbonate, palladium acetate and 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine at the temperature of 80-100 ℃ to obtain an eighth compound;
and dissolving the eighth compound in diethyl ether, and reacting at normal temperature under the combined catalysis of potassium hexacyanoferrate and sodium hydroxide to obtain the PDI free radical derivative.
9. The method for preparing a graphene spin field effect transistor according to claim 6, wherein the method for preparing a PDI radical derivative comprises:
dissolving 5- (3-hydroxypropyl) -1H-benzisoquinoline-1, 3 (2H) -dione in diethylene glycol dimethyl ether, and reacting under the combined catalysis of 2,5 dichloro-cyanobenzene and potassium tert-butoxide at 120-140 ℃ to obtain a ninth compound;
dissolving the ninth compound and the 1, 8-diazacyclo in toluene, cooling the mixture to 0 ℃, then dissolving the mixture with triphenylphosphine and ammonia water in pyridine, and reacting at room temperature to obtain a tenth compound;
dissolving the tenth compound in tetrahydrofuran, and reacting under the catalysis of potassium hydroxide to obtain an eleventh compound;
and dissolving the eleventh compound in diethyl ether, and reacting at normal temperature under the combined catalysis of potassium hexacyanoferrate and sodium hydroxide to obtain the PDI free radical derivative.
10. The method for manufacturing a graphene spin field effect transistor according to any one of claims 6 to 9, wherein step S4 includes:
mixing the silicon wafer containing the graphene dot electrode pairs with a sufficient amount of 1- (3-dimethylaminopropyl) -3-2-ethylcarbodiimide hydrochloride and a PDI free radical derivative to obtain a mixed system;
placing the mixed system in a nitrogen atmosphere, injecting anhydrous pyridine into the mixed system, and standing;
washing and drying the silicon wafer containing the graphene point electrode pairs to obtain the graphene spin field effect transistor;
and/or, the preparation method further comprises:
and arranging a protective layer on one side of the graphene point electrode pair, which is far away from the silicon substrate, so that the gold electrode, the magnetic electrode and the graphene point electrode pair are covered by the protective layer.
CN202311365713.3A 2023-10-20 2023-10-20 PDI free radical derivative and graphene spin field effect transistor Pending CN117263937A (en)

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