Capacitance-inductance bifunctional device based on a fulvalene molecule and method for manufacturing the same

Abstract

The application relates to the technical field of molecular devices, in particular to a capacitance-inductance dual-function device based on a helicene molecule and a preparation method thereof. The device comprises a first graphene dot electrode, a helicene molecule and a second graphene dot electrode, the first graphene dot electrode and the second graphene dot electrode form a graphene dot electrode pair, and the helicene molecule is connected between the graphene dot electrode pair; the helicene molecule is switched between capacitance and inductance effects by changing the voltage change rate of alternating current applied to the helicene molecule; when the voltage change rate of the alternating current is 0.1-1.0 V / s, the helicene molecule has inductance effect; when the voltage change rate of the alternating current is greater than or equal to 10 V / s, the helicene molecule has capacitance effect. The preparation method provided by the application is prepared on the basis of a graphene single-molecule field effect transistor, realizes significant miniaturization of the device size, and exhibits high integration.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of molecular device, and in particular to a capacitance-inductance dual-function device based on a chiralene molecule and a preparation method thereof. BACKGROUND

[0002] With the cross-fusion of nanotechnology and molecular engineering, molecular electronics has entered a rapid development stage in recent years due to its value in breaking through the limitations of Moore's Law and realizing the ultimate miniaturization of electronic devices. As the core research object of molecular electronics, single-molecule devices, relying on their atomic-level precise controllability of structure and unique quantum effects at the nanoscale, have shown an irreplaceable application prospect in the fields of ultra-high-density storage, micro-sensing, low-power circuits, etc. The research of traditional single-molecule electronic devices is mostly focused on relatively mature devices such as switches and rectifiers. However, as the core elements of inductance and capacitance in electronic circuits, which constitute the key modules of filter networks, timing control, and energy buffering, the research on single-molecule scale has been lagging for a long time, and this research gap has gradually become an important bottleneck restricting the integration of complex functions of single-molecule circuits.

[0003] Inductance realizes signal coupling, frequency selection, and current smoothing through magnetic field energy storage, and capacitance completes charge storage, signal filtering, and voltage stabilization through electric field energy storage, both of which support almost all signal processing and energy management functions of electronic devices. However, when the device size is reduced to the single-molecule level, its electrical characteristics differ fundamentally from macroscopic systems. In single-molecule systems, electron transport no longer follows the classical Ohm's law, but is dominated by quantum mechanisms such as quantum tunneling effect, electron-phonon coupling, and intramolecular charge redistribution, which makes the inductance of single-molecule inductance and the capacitance of single-molecule capacitance vary with frequency significantly different from macroscopic metal coils and dielectric capacitors.

[0004] Graphene, as a two-dimensional material with excellent electrical properties, has unique electronic structure and high conductivity, making it an ideal material for constructing single-molecule devices. However, there is currently no effective strategy for integrating functional molecules in graphene electrode systems to realize inductance and capacitance dual-function. SUMMARY

[0005] The present application aims to at least solve one of the technical problems in the related art. To this end, the first object of the present application is to provide a capacitance-inductance dual-function device based on a chiralene molecule, and the second object of the present application is to provide a preparation method of the capacitance-inductance dual-function device based on a chiralene molecule.

[0006] To achieve the first object, the technical solution adopted by the present application is:

[0007] A device with capacitance and inductance dual functions based on a chiral molecule, comprising a first graphene dot electrode, a chiral molecule and a second graphene dot electrode, the first graphene dot electrode and the second graphene dot electrode form a graphene dot electrode pair, the chiral molecule is connected between the graphene dot electrode pair, the structure of the chiral molecule is as follows:

[0008] ;

[0009] The chiral molecule is switched between capacitance and inductance effects by changing the voltage change rate of the alternating current applied to the chiral molecule;

[0010] When the voltage change rate of the alternating current is 0.1-1.0 V / s, the chiral molecule has inductance effect; when the voltage change rate of the alternating current is greater than or equal to 10 V / s, the chiral molecule has capacitance effect;

[0011] A single chiral molecule is connected between the first graphene dot electrode and the second graphene dot electrode.

[0012] In the design of inductors and capacitors, how to utilize the rigid and conductive helical conjugated structure is crucial to the design of coiled single-molecule wires. A helicene is a polycyclic aromatic compound formed by the ortho-fusion of benzene rings or other aromatic rings, which exhibits rigidity and helical geometry due to intramolecular steric repulsion of the two terminal rings. The delocalized helical pi-conjugated system in helicene provides two charge pathways within the molecule, one through the curled backbone and the other through the interlayer intramolecular pi-pi stacking. These two charge paths correspond to different electrical elements: inductors and capacitors. The main difference between them is the response behavior when an alternating current is applied to the electrical element. Capacitors allow alternating current to pass through, while inductors prevent alternating current from passing through. Inductors exhibit a delayed current response relative to the applied alternating voltage, which is known as the phenomenon of current lag. Specifically, the current changes more slowly than the voltage. In contrast, capacitors exhibit a current lead effect, which is characterized by a faster response of the current change than the voltage when an alternating electric field is applied. Based on the above principle, the present application takes helicene molecules with rigid and conductive conjugated structures as the core functional molecules, and connects them between the graphene dot electrode pairs through the method of chemical self-assembly, to form a helicene molecule-based capacitor-inductor dual-function device. When the voltage change rate of the alternating current is 0.1-1.0 V / s, the charges selectively flow through the conjugated helical backbone to form a transfer path, generating a ring current and exhibiting the inductor behavior of current lag, and the helicene molecule has an inductive effect; when the voltage change rate of the alternating current is greater than or equal to 10 V / s, the charge flow in the device is hindered, and the charges can move vertically between the two layers through the intramolecular pi-pi stacking effect to form a pi-pi stacking path, and the helicene molecule has a capacitive effect. The ability to adjust the voltage change rate of the alternating current to manipulate the charge transport path enables the helicene molecule-based capacitor-inductor dual-function device to switch the function of the helicene molecule between inductors and capacitors.

[0013] Preferably, the first graphene dot electrode and the second graphene dot electrode are single-layer graphene dot electrodes.

[0014] Preferably, the first graphene dot electrode and the second graphene dot electrode are array electrodes.

[0015] Preferably, the first graphene dot electrode and the second graphene dot electrode are nanogap electrodes.

[0016] To achieve the second object, the technical solution adopted by the present application is:

[0017] The preparation method of the helicene molecule-based capacitor-inductor dual-function device, for preparing the helicene molecule-based capacitor-inductor dual-function device described in any one of the above, comprises the following steps:

[0018] S100, preparing a metal oxide dielectric layer on a substrate by a thermal evaporation method;

[0019] S200, preparing a single-layer graphene on a copper foil by a vapor deposition method, transferring the single-layer graphene to the metal oxide dielectric layer to obtain a graphene dielectric layer;

[0020] S300, preparing a graphene dot electrode pair on the graphene dielectric layer by an oxygen plasma etching and an electrical burnout method;

[0021] S400, placing the graphene dot electrode pair in a pyridine solution containing a fulle ne molecule and a condensing agent, self-assembling the fulle ne molecule and the graphene dot electrode pair to obtain a capacitive-inductive dual-function device based on the fulle ne molecule.

[0022] Preferably, in step S100, the metal oxide dielectric layer is selected from an aluminum oxide dielectric layer.

[0023] Preferably, the thickness of the aluminum oxide dielectric layer is 30-40 nm.

[0024] Preferably, in step S100, the substrate is selected from a silicon wafer.

[0025] Preferably, in step S400, the synthesis route of the fulle ne molecule is as shown in the following figure:

[0026] .

[0027] Preferably, in step S400, the condensing agent is selected from 1-(3-dimethylaminopropyl)-3-2 ethyl carbodiimide hydrochloride.

[0028] The above one or more technical solutions in the embodiments of the present application have at least one of the following technical effects:

[0029] The application provides a capacitance and inductance dual-function device based on a chiralene molecule, which comprises a first graphene dot electrode, the chiralene molecule and a second graphene dot electrode, the first graphene dot electrode and the second graphene dot electrode form a graphene dot electrode pair, and the chiralene molecule is connected between the graphene dot electrode pair; the chiralene molecule is switched between capacitance and inductance effects by changing a voltage change rate of alternating current applied to the chiralene molecule; when the voltage change rate of the alternating current is 0.1-1.0 V / s, the chiralene molecule has inductance effect; and when the voltage change rate of the alternating current is greater than or equal to 10 V / s, the chiralene molecule has capacitance effect. The delocalized helical π-conjugated system in the chiralene molecule provides two charge transfer paths in the molecule, one through the curled skeleton and the other through interlayer intramolecular π-π stacking. The two charge transfer paths ensure the emergence of the capacitance effect and the inductance effect of the device, and the two effects can be switched by simply changing the voltage change rate of the applied alternating current. The existence of the two charge transfer paths and the switching mechanism provide a new idea for designing and realizing a single-molecule logic device, and help to accurately control the charge transfer path, so that the inductance and capacitance behaviors of the chiralene molecule under different voltage change rates of alternating current are realized.

[0030] Meanwhile, the application provides a preparation method of the capacitance and inductance dual-function device based on the chiralene molecule, which is prepared based on a graphene single-molecule field effect transistor, realizes significant miniaturization of the device size, and exhibits high integration degree. The characteristics provide a new idea for miniaturization and high-density integration of a functional chip.

[0031] Additional aspects and advantages of the application will be made apparent by the following description. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 FIG. 1 is a structural schematic diagram of a capacitance and inductance dual-function device based on a chiralene molecule provided by an embodiment of the application.

[0033] Figure 2 FIG. 3 is a schematic diagram of two controllable charge transport paths of a chiralene molecule provided by an embodiment of the application.

[0034] Figure 3 FIG. 4 is a current-voltage (I-V) curve diagram of a capacitance and inductance dual-function device based on a chiralene molecule provided by an embodiment 2 of the application when different voltage change rates (0.1 V / s, 1.0 V / s, 10 V / s and 100 V / s) are applied.

[0035] Figure 4 FIG. 5 is an I-V curve diagram of a capacitance and inductance dual-function device based on a chiralene molecule provided by an embodiment 2 of the application under different scanning rates (0.1 V / s and 100 V / s).

[0036] Figure label:

[0037] 1. First graphene point electrode; 2. Helene molecule; 3. Second graphene point electrode. Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. The following embodiments are used to illustrate this invention, but cannot be used to limit the scope of this invention.

[0039] like Figure 1 As shown, a device based on helicene molecules with both capacitive and inductive functions includes a first graphene point electrode 1, a helicene molecule 2, and a second graphene point electrode 3. The first graphene point electrode 1 and the second graphene point electrode 3 form a graphene point electrode pair, and the helicene molecule 2 is connected between the graphene point electrode pairs. The structural formula of the helicene molecule 2 is shown below:

[0040] ;

[0041] By changing the rate of change of the alternating current applied to the helicene molecule, the helicene molecule can switch between capacitive and inductive effects.

[0042] When the voltage change rate of alternating current is 0.1–1.0 V / s, charge selectively flows through the helical skeleton to form a conjugate helical main chain transfer path (e.g., Figure 2 As shown), it generates a toroidal current and exhibits inductor behavior with current hysteresis; helicene molecules have an inductive effect; when the voltage change rate of alternating current is greater than or equal to 10V / s, the charge flow within the device is impeded, and the charge can move vertically between the two layers through the intramolecular π-π stacking effect to form π-π stacking paths (such as...). Figure 2 As shown in the figure, helicene molecules exhibit a capacitance effect.

[0043] In the following embodiments, unless otherwise specified, the experimental methods used are conventional methods, and the materials and reagents used are commercially available, unless otherwise specified, and are carried out in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions.

[0044] Example 1

[0045] The synthetic route for helicene molecules is shown below:

[0046] ;

[0047] The preparation process is as follows:

[0048] I. Preparation of compound 2.

[0049] 25℃, nitrogen atmosphere, to the three-necked flask was added compound 1 (100 mmol), ethylene glycol (110 mmol), trifluoromethanesulfonic acid (200 mmol), toluene (500 mL), 110℃ reflux 10h. The resulting product was filtered and purified by column chromatography to obtain compound 2, which 1 H NMR, 13 C NMR and TOF-ESI+ data are as follows:

[0050] 1 H NMR (500 MHz, CDCl3): δ 7.72 (d, J = 2.3 Hz, 1H), 7.40 (dd, J = 8.1, 2.3 Hz, 1H), 7.09 (dt, J = 8.2, 1.0 Hz, 1H), 5.34 (t, J = 3.7 Hz, 1H), 3.96-3.82 (m, 4H), 3.09 (ddd, J = 16.5, 3.7, 1.0 Hz, 1H), 3.02 (ddd, J = 16.5, 3.7, 1.0 Hz, 1H);

[0051] 13 C NMR (125 MHz, CDCl3): δ 136.62, 134.46, 130.95, 130.69, 122.56, 121.61, 104.63, 64.92, 39.38;

[0052] TOF-ESI+ (m / z): C 10 H 10 Br2O2322.00.

[0053] II. Preparation of compound 3.

[0054] 25℃, nitrogen atmosphere, to the three-necked flask was added compound 2 in 1,4-dioxane solution (250 mL) with a concentration of 0.2 mmol / mL, (55 mmol), potassium acetate (300 mmol), PdCl2(dppf)2 (0.5 mmol), 100℃ reaction 5h, rotary evaporation to concentrate the solvent, and separated by silica gel column chromatography to obtain compound 3, which 1 HNMR、 13 C NMR and TOF-ESI+ data are as follows:

[0055] 1H NMR (500MHz, CDCl3): δ 7.52(d, J=2.2Hz, 1H), 7.36(dd, J=7.1, 2.2Hz, 1H), 7.12(dt, J=7.4, 1.0Hz, 1H), 5 .30(t, J=3.6Hz, 1H), 3.96–3.81(m, 4H), 3.06(dd, J=3.6, 1.0Hz, 2H), 1.24(s, 9H);

[0056] 13 C NMR (125MHz, CDCl3): δ 141.34, 135.21, 134.00, 131.91, 131.20, 122.30, 105.12, 83.78, 64.92, 40.41, 24.84;

[0057] TOF-ESI+ (m / z): C 16 H 22 BBrO4369.06.

[0058] III. Preparation of compound 4.

[0059] Compound 3 (40 mmol) was added to a two-necked flask at 25 °C under a nitrogen atmosphere. After adding 20 mmol of K₂CO₃ (100 mmol) and 0.2 mmol of Pd(PPh₃)₄, a toluene-water mixture (110 ml) (toluene to water volume ratio 5:1) was added. The mixture was heated to 110 °C and refluxed for 30 h. After cooling to 25 °C, the reaction mixture was poured into water and extracted three times with dichloromethane (50 ml). The organic phase was collected, dried over anhydrous sodium sulfate, and the solvent was removed to obtain the crude product. The crude product was then purified by silica gel column chromatography to give compound 4. 1 H NMR, 13 The C NMR and TOF-ESI+ data are as follows:

[0060] 1 H NMR (500MHz, CDCl3): δ 8.28–8.24 (m, 1H), 8.00–7.94 (m, 2H), 7.66 (d, J=1.9Hz, 1H), 7.66–7.54 (m, 3H), 7.50 (dd, J=9.2, 2.4Hz, 1H), 7.45– 7.38(m, 1H), 7.14(2H), 5.17(t, J=3.8Hz, 2H), 3.96–3.82(m, 8H), 3.15(2H), 3.07–3.02(m, 1H), 3.05–2.98(m, 1H);

[0061] 13C NMR (125 MHz, CDC13): δ 137.86, 137.26, 136.46, 135.61, 134.59, 134.37, 133.80, 132.40, 132.09, 131.39, 131.34, 131.03, 129.86, 129.84, 129.40, 127.86, 127.42, 127.34, 125.93, 125.14, 119.77, 119.57, 104.95, 104.91, 64.93, 38.54, 38.49;

[0062] TOF-ESI+(m / z): C 30 H 26 Br2O4610.34.

[0063] IV. Preparation of compound 5.

[0064] After adding compound 4 in hexafluoroisopropanol (10 mL) with a concentration of 0.5 mmol / mL at 25 °C under nitrogen condition; cooling to 0 °C, adding trifluoromethanesulfonic acid (0.5 mmol), then stirring for 15 min, stopping the reaction with phosphate buffer with pH = 7. Then extracting with dichloromethane (DCM) for three times, collecting the organic layer, washing the organic layer with saturated brine, and drying with anhydrous sodium sulfate, then removing the solvent by rotary evaporation to obtain the crude product, further separating and purifying the crude product by silica gel column chromatography to obtain compound 5, which 1 H NMR, 13 C NMR and TOF-ESI+ data are as follows:

[0065] 1 H NMR (500 MHz, CDC13): δ 8.68 (d, J = 1.7 Hz, 1H), 8.58 - 8.51 (m, 3H), 8.21 (d, J = 8.3 Hz, 1H), 8.11 (d, J = 8.8 Hz, 1H), 8.03 (dd, J = 9.7, 8.7 Hz, 2H), 7.95 (dd, J = 9.2, 1.5 Hz, 2H), 7.88 (dd, J = 8.1, 2.2 Hz, 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.71 (dd, J = 8.3, 2.2 Hz, 2H);

[0066] 13C NMR (125MHz, CDCl3): δ 133.51, 133.28, 132.30, 132.21, 131.99, 131.86, 130.90, 130.65, 130.59, 130.09, 129.81, 129.33, 129.29, 128.90, 128.15, 127.81, 127.53, 127.42, 127.41, 127.34, 127.15, 126.93, 125.84, 122.79, 120.05, 119.69;

[0067] TOF-ESI+(m / z): C 26 H 14 Br2486.21.

[0068] V. Preparation of compound 6.

[0069] At 25°C, under a nitrogen atmosphere, a toluene solution (10 mmol) containing compound 5 at a concentration of 0.1 mmol / mL was added to a three-necked flask. (11 mmol), potassium acetate (60 mmol), PdCl2(dppf)2 (0.1 mmol), heated to 100 °C and reacted for 5 h. The solvent was concentrated by rotary evaporation, and then compound 6 was obtained by silica gel column chromatography. 1 H NMR, 13 The C NMR and TOF-ESI+ data are as follows:

[0070] 1 H NMR (500MHz, CDCl3): δ 8.99(d, J=1.8Hz, 1H), 8.58–8.51(m, 3H), 8.11(dd, J=8.8, 0.7Hz, 1H), 8.07–8.00(m, 2H), 7.95(dd, J=8.8, 1.3Hz, 2H), 7.91–7.77(m, 4H), 7.71(dd, J=8.4, 2.6Hz, 1H), 1.24(s, 10H);

[0071] 13 C NMR (125MHz, CDCl3): δ 135.20, 133.24, 133.15, 132.80, 132.73, 132.32, 132.21, 131.99, 130.65, 130.59, 130.26, 129.81, 129.29 , 127.81, 127.66, 127.55, 127.43, 127.41, 127.34, 126.93, 126.70, 125.84, 122.83, 119.69, 83.57, 24.84;

[0072] TOF-ESI+(m / z): C 32 H 26 BBrO2533.27.

[0073] VI. Preparation of Compound 7.

[0074] Compound 6 (10 mmol) was added to a two-necked flask at 25 °C under a nitrogen atmosphere. After adding 10 mmol of K₂CO₃ (50 mmol) and 0.1 mmol of Pd(PPh₃)₄, a toluene-water mixture (60 ml) (toluene to water volume ratio 5:1) was added. The mixture was heated to 110 °C and refluxed for 30 h. After cooling to 25 °C, the reaction mixture was poured into water and extracted three times with dichloromethane (50 ml). The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed to obtain the crude product. The crude product was then purified by silica gel column chromatography to give compound 7. 1 H NMR, 13 The C NMR and TOF-ESI+ data are as follows:

[0075] 1 H NMR (500MHz, CDCl3): δ 8.58–8.51(m, 3H), 8.47(d, J=1.8Hz, 1H), 8.17(d, J=8.8Hz, 1H), 8.13–8.00(m, 4H), 7.95 (dd, J=9.0, 2.1Hz, 2H), 7.88 (dd, J=8.0, 2.2Hz, 1H), 7.79 (dd, J=8.1, 0.8Hz, 1H), 7.71(d d, J=8.4, 2.6Hz, 1H), 7.60–7.54 (m, 2H), 7.20 (dt, J=8.1, 1.0Hz, 2H), 5.20 (t, J=4.9Hz, 1 H), 3.17 (td, J=5.6, 4.8Hz, 2H), 2.65 (tt, J=7.8, 1.1Hz, 2H), 1.82 (tt, J=7.9, 5.8Hz, 2H);

[0076] 13C NMR (125 MHz, CDC13): δ 156.39, 142.19, 139.30, 138.39, 133.53, 133.22, 132.58, 132.32, 132.21, 131.99, 130.65, 130.59, 130.20, 129.81, 129.71, 129.29, 129.24, 127.81, 127.75, 127.67, 127.52, 127.42, 127.41, 127.34, 127.06, 126.93, 125.84, 125.31, 124.57, 122.79, 119.69, 79.54, 40.36, 33.59, 29.99, 28.30:

[0077] TOF-ESI+(m / z): C 40 H 34 BrNO2640.62.

[0078] Seven, preparing compound 8.

[0079] Into a two-mouth flask was added compound 7 (10 mmol), cuprous iodide (2 mmol), Pd(PPh3)2Cl2(1 mmol) and dissolved with anhydrous tetrahydrofuran (10 mL) at 25°C under nitrogen atmosphere, then added trimethylsilyl acetylene (40 mmol) and diisopropyl ethylamine (40 mmol) after cooling to 0°C, then warmed to 60°C, reacted for 48 h, extracted with ether, collected the organic layer, washed with saturated brine, dried with anhydrous sodium sulfate, filtered, concentrated by rotary evaporation, the obtained crude product was purified by silica gel column chromatography to obtain compound 8, whose 1 H NMR, 13 C NMR and TOF-ESI+ data are as follows:

[0080] 1H NMR (500 MHz, CDC13): δ 8.58-8.53 (m, 3H), 8.47 (d, J = 1.8 Hz, 1H), 8.17 (d, J = 8.8 Hz, 1H), 8.13-8.04 (m, 2H), 8.02 (s, 1H), 8.02-7.97 (m, 1H), 7.97-7.92 (m, 2H), 7.91-7.85 (m, 1H), 7.79 (dd, J = 8.1, 0.7 Hz, 1H), 7.61-7.54 (m, 3H), 7.20 (dq, J = 8.1, 1.3 Hz, 2H), 5.20 (t, J = 4.9 Hz, 1H), 3.17 (td, J = 5.6, 4.8 Hz, 2H), 2.65 (tt, J = 7.8, 1.1 Hz, 2H), 1.82 (tt, J = 7.9, 5.8 Hz, 2H), 0.25 (s, 7H);

[0081] 13 C NMR (125 MHz, CDC13): δ 156.39, 142.19, 139.30, 138.39, 133.53, 133.28, 132.58, 132.32, 131.83, 131.57, 131.01, 130.95, 130.69, 130.20, 129.71, 129.24, 128.42, 127.75, 127.67, 127.52, 127.43, 127.33, 127.06, 126.93, 125.84, 125.31, 124.57, 122.86, 120.92, 103.81, 100.20, 79.54, 40.36, 33.59, 29.99, 28.30;

[0082] TOF-ESI+(m / z): C 45 H 43 NO2Si 657.93.

[0083] Eighth, preparing compound 9.

[0084] 25 °C, under nitrogen atmosphere, in a round bottom flask was added compound 8 (5 mmol), cooled to 0 °C, added tetrahydrofuran (25 mL) and methanol (25 mL) to dissolve, then added K2CO3 (25 mmol). Warmed to 25 °C, stirred for 12 h, the reaction solution was extracted with chloroform, the organic layer was collected, washed with saturated brine three times, then dried with anhydrous sodium sulfate, filtered, concentrated by rotary evaporation to obtain the crude product, which was purified by silica gel column chromatography to obtain compound 9, which 1 H NMR, 13 C NMR and TOF-ESI+ data are as follows:

[0085] 1 H NMR (500 MHz, CDC13): δ 8.60 (d, J = 2.5 Hz, 1H), 8.57 - 8.53 (m, 2H), 8.47 (d, J = 1.8 Hz, 1H), 8.17 (d, J = 8.8 Hz, 1H), 8.13 - 8.05 (m, 2H), 8.05 - 7.97 (m, 2H), 7.97 - 7.92 (m, 2H), 7.91 - 7.85 (m, 1H), 7.79 (dd, J = 8.1, 0.7 Hz, 1H), 7.60 (dd, J = 6.8, 2.2 Hz, 1H), 7.60 - 7.54 (m, 2H), 7.20 (dt, J = 8.1, 1.0 Hz, 2H), 5.20 (t, J = 4.9 Hz, 1H), 3.28 (s, 1H), 3.17 (td, J = 5.6, 4.8 Hz, 2H), 2.65 (tt, J = 7.8, 1.1 Hz, 2H), 1.82 (tt, J = 7.9, 5.8 Hz, 2H);

[0086] 13 C NMR (125 MHz, CDC13): δ 156.39, 142.19, 139.30, 138.39, 133.53, 133.28, 132.58, 132.34, 132.32, 132.08, 131.71, 131.07, 130.75, 130.69, 130.20, 129.71, 129.24, 127.75, 127.67, 127.52, 127.46, 127.43, 127.33, 127.06, 126.93, 125.84, 125.31, 124.57, 122.86, 119.98, 79.54, 78.93, 78.30, 40.36, 33.59, 29.99, 28.30;

[0087] TOF-ESI+(m / z): C 42 H 35 NO2585.75.

[0088] IX. Preparation of compound 10.

[0089] 25 °C, nitrogen atmosphere, into the flask was added compound 7 (5 mmol), cuprous iodide (1 mmol) Pd(PPh3)2Cl2(0.5 mmol), then added anhydrous tetrahydrofuran (10 mL) to dissolve, to obtain a mixed solution, after cooling to 0 °C, compound 9 (50 mmol) and diisopropyl ethylamine (20 mmol) were added, and the temperature was raised to 60 °C, and the reaction was carried out for 48 h. The reaction solution was extracted with ether, the organic layer was collected, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated by rotary evaporation to obtain a crude product, which was purified by silica gel column chromatography to obtain compound 10, and 1 H NMR, 13 C NMR and TOF-ESI+data are as follows:

[0090] 1 H NMR (500 MHz, CDCl3): δ 8.58 (d, J = 2.0 Hz, 1H), 8.56-8.53 (m, 2H), 8.47 (d, J = 1.8 Hz, 1H), 8.17 (d, J = 8.8 Hz, 1H), 8.13-8.04 (m, 2H), 8.02 (s, 1H), 8.02-7.97 (m, 1H), 7.97-7.92 (m, 2H), 7.91-7.85 (m, 1H), 7.79 (dd, J = 8.1, 0.7 Hz, 1H), 7.61-7.54 (m, 3H), 7.20 (dt, J = 8.1, 1.0 Hz, 2H), 5.20 (t, J = 4.9 Hz, 1H), 3.17 (td, J = 5.6, 4.8 Hz, 2H), 2.65 (tt, J = 7.8, 1.1 Hz, 2H), 1.82 (tt, J = 7.9, 5.8 Hz, 2H);

[0091] 13 C NMR (125 MHz, CDCl3): δ 156.39, 142.19, 139.30, 138.39, 133.53, 133.28, 132.58, 132.37, 132.32, 131.93, 131.71, 130.99, 130.70, 130.69, 130.20, 129.71, 129.24, 127.75, 127.67, 127.55, 127.52, 127.43, 127.33, 127.06, 126.93, 125.84, 125.31, 124.57, 122.86, 120.58, 89.52, 79.54, 40.36, 33.59, 29.99, 28.30;

[0092] TOF-ESI+(m / z): C 82 H68 N2O 411 45.46.

[0093] X. Preparation of compound 11.

[0094] To a flask, compound 10 (1 mmol) and a solution of trifluoroacetic acid in dichloromethane (10 mL) with a volume concentration of 50% (v / v) were added at 25°C under a nitrogen atmosphere, after stirring for 2 h, saturated sodium bicarbonate solution was added, extracted, and repeatedly washed until neutral, the collected organic layer was evaporated to remove the solvent to obtain compound 11, which 1 H NMR, 13 C NMR and TOF-ESI+ data are as follows:

[0095] 1 H NMR (500 MHz, CDC13): δ 8.58 (d, J = 2.1 Hz, 1H), 8.56 - 8.53 (m, 2H), 8.47 (d, J = 1.8 Hz, 1H), 8.17 (d, J = 8.8 Hz, 1H), 8.13 - 8.05 (m, 2H), 8.05 - 7.97 (m, 2H), 7.97 - 7.92 (m, 2H), 7.88 (dd, J = 8.1, 2.1 Hz, 1H), 7.79 (dd, J = 8.0, 0.8 Hz, 1H), 7.61 - 7.54 (m, 3H), 7.20 (dt, J = 8.1, 1.0 Hz, 2H), 2.77 (tt, J = 6.3, 5.4 Hz, 2H), 2.65 (tt, J = 7.6, 1.1 Hz, 2H), 1.83 (tt, J = 7.7, 5.4 Hz, 2H), 1.60 (d, J = 12.6 Hz, 1H);

[0096] 13 C NMR (125 MHz, CDC13): δ 141.74, 139.30, 138.39, 133.53, 133.28, 132.58, 132.37, 132.32, 131.93, 131.71, 130.99, 130.70, 130.69, 130.20, 129.71, 129.21, 127.75, 127.67, 127.55, 127.52, 127.43, 127.33, 127.06, 126.93, 125.84, 125.31, 124.57, 122.86, 120.58, 89.52, 41.70, 33.91, 33.06;

[0097] TOF-ESI+(m / z): C 72 H 52 N2 945.22.

[0098] Example 2

[0099] A device based on a spiro molecule is prepared, and the process is as follows:

[0100] I. An aluminum oxide dielectric layer is prepared on a silicon substrate.

[0101] A photoresist is spin-coated on a silicon wafer (silicon substrate) with a size of 1 cm x 1 cm, a mask plate is placed on the spin-coated silicon wafer using a photoetching machine to perform photoetching, and then the photoetched silicon wafer is transferred to a vacuum thermal evaporation device to evaporate chromium with a thickness of 6-9 nm and gold with a thickness of 30-35 nm, thereby obtaining a lead electrode. The photoresist is spin-coated again on the lead electrode, and then the silicon wafer is placed on the stage of the photoetching machine, the mask plate is replaced, and photoetching is performed to obtain a bottom gate. After the bottom gate is prepared, the bottom gate is placed in a vacuum thermal evaporation device to evaporate an aluminum film with a thickness of 30-40 nm on the surface of the bottom gate, and then the bottom gate is soaked in an acetone solution to remove the photoresist, thereby obtaining an aluminum oxide dielectric layer.

[0102] II. A graphene dielectric layer is prepared on the aluminum oxide dielectric layer, and a metal electrode is prepared on the graphene dielectric layer.

[0103] A single-layer graphene is obtained on a clean copper foil by chemical vapor deposition; methyl methacrylate (PMMA 950) is spin-coated on the single-layer graphene, and then the graphene is baked on a heating table at 180°C for 2 min. The back of the copper foil is etched by oxygen plasma for 3 s to remove the excess PMMA and graphene, thereby obtaining a PMMA-single-layer graphene-copper foil. Then, the PMMA-single-layer graphene-copper foil is cut into small pieces, transferred to a ferric chloride solution to dissolve the copper foil, and a PMMA-single-layer graphene film is obtained. After the PMMA-single-layer graphene film is soaked in a hydrochloric acid solution, a water solution, and a potassium hydroxide solution, it is transferred to the aluminum oxide dielectric layer, and after standing, air-drying, and removing the photoresist, a graphene dielectric layer is obtained.

[0104] A photoetching strip is performed on the graphene dielectric layer, and the excess single-layer graphene is removed by oxygen plasma etching, thereby obtaining a bottom piece with a graphene strip; an electrode is photoetched on the bottom piece, and 8-10 nm of chromium and 60-80 nm of gold are evaporated, thereby obtaining a metal electrode.

[0105] III. A graphene point electrode is constructed using the graphene dielectric layer.

[0106] In the photoetching of the electrode with the graphene strip, photoresist is spin-coated on the substrate, and graphene strips are photoetched by using a customized strip mask plate. After exposure and development, the strip-shaped photoresist is left to protect part of the graphene, and the graphene is etched by 5s oxygen plasma again. The remaining exposed graphene is removed by the oxygen plasma etching process. Then, the graphene array electrode with a central graphene strip is obtained by removing the photoresist by acetone immersion. The graphene array electrode is obtained by sequentially evaporating 8-10 nm of chromium and 60-80 nm of gold on the aforementioned substrate by thermal evaporation, and removing the photoresist by acetone immersion. The graphene nanogap point electrode array is obtained by electron beam exposure and etching of the dashed line with a length of 150 nm and a width of 5 nm, followed by development in methyl isobutyl ketone (MIBK) diluted with isopropyl alcohol (the volume ratio of MIBK to isopropyl alcohol is 1:3), fixing in isopropyl alcohol, and oxygen plasma etching and electrical burnout.

[0107] In this embodiment, the graphene nanogap point electrode array includes 169 pairs of graphene point electrodes.

[0108] IV. Self-assembly of a single fulvalene molecule with a pair of graphene point electrodes to obtain a capacitive-inductive dual-functional device based on the fulvalene molecule.

[0109] At 25℃, the fulvalene molecule (16.5mg) is added to a three-necked flask, and then anhydrous pyridine (10ml) is added to dissolve the fulvalene molecule. Then, the pair of graphene point electrodes is placed in the three-necked flask, and 1-(3-dimethylaminopropyl)-3-2 ethyl carbodiimide hydrochloride (30mg) is added to the three-necked flask. Under a nitrogen atmosphere, the reaction is carried out for 48h to form an amide covalent bond between the -NH2 at both ends of the fulvalene molecule and the -COOH at the end of the graphene point electrode. The device is removed from the three-necked flask, rinsed with deionized water and ethanol three times respectively, and dried with nitrogen to obtain the capacitive-inductive dual-functional device based on the fulvalene molecule. The current-voltage (I-V) characteristic curve of the device is tested by applying alternating current with different voltage change rates to the device, and the process is as follows:

[0110] The capacitive-inductive dual-functional device based on the fulvalene molecule is placed on the light detection table of the Physical Property Measurement System (PPMS), and the electrical probe is connected to the two metal electrodes of the device to form an electrical circuit. The alternating current with different voltage change rates (0.1V / s, 1V / s, 10V / s, and 100V / s, respectively) is used for testing, and the results are as follows: Figure 3As shown in the figure, when the voltage rate of change is 1V / s, the current response is accompanied by a significant current hysteresis effect, that is, the current drops to zero at a non-zero positive voltage, which demonstrates the characteristics of an inductor, in which the voltage reaches its minimum faster than the current, when the voltage rate of change is reduced to 0.1V / s, the current hysteresis effect is still observed; however, when the voltage rate of change is increased to 10V / s, the current leads effect replaces the current hysteresis effect, and the current drops to zero at a non-zero negative voltage, which demonstrates the characteristics of a capacitor. By further increasing the frequency of the device to 100V / s, the current advance is more obvious, and an almost pure single-molecule capacitor is obtained.

[0111] The current-voltage (I-V) relationship of the device based on the helicene molecule at different scan rates is as shown in the figure Figure 4 As shown in the figure, compared with the zero point identified by the dashed line in the figure, at a low scan rate (such as 0.1V / s), the change of the current lags behind the change of the voltage. Specifically, when the voltage increases from a negative value to a positive value, the current has already begun to rise before the voltage reaches zero, but the voltage has not completely reached zero when the voltage reaches zero, and the forward scan curve is on the right side of the dashed line. This hysteresis phenomenon is a typical characteristic of an inductor, indicating that the charge is mainly transmitted through the helical conjugated main chain of the molecule, similar to the ring current in an inductor; at a high scan rate (such as 100V / s), the change of the current precedes the change of the voltage, specifically, when the voltage decreases from a positive value to a negative value, the current has already begun to drop before the voltage reaches zero, and the current reaches zero when the voltage has not completely reached zero, and the reverse scan curve appears on the right side of the dashed line, which is a typical characteristic of a capacitor, indicating that the charge is mainly transmitted through the intramolecular π-π stacking path, similar to the electric field effect in a capacitor.

[0112] From the above detection results, it can be known that the device based on the helicene molecule provided by the application simultaneously has the characteristics of a capacitor and an inductor.

[0113] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the application, but not to limit it; although the application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the application.

Claims

1. A device based on the electric capacitance and inductance duality of a fulvalene molecule, characterized in that, The device comprises a first graphene dot electrode, a fulvalene molecule and a second graphene dot electrode, the first graphene dot electrode and the second graphene dot electrode form a graphene dot electrode pair, the fulvalene molecule is connected between the graphene dot electrode pair, and the structural formula of the fulvalene molecule is as follows: ； The fulvalene molecule is switched between the capacitance and inductance effects by changing the voltage change rate of the alternating current applied to the fulvalene molecule; When the voltage change rate of the alternating current is 0.1-1.0 V / s, the fulvalene molecule has an inductance effect; when the voltage change rate of the alternating current is greater than or equal to 10 V / s, the fulvalene molecule has a capacitance effect; A single fulvalene molecule is connected between the first graphene dot electrode and the second graphene dot electrode.

2. The device based on a molecule of a chiralene according to claim 1, characterized in that, The first graphene dot electrode and the second graphene dot electrode are single-layer graphene dot electrodes.

3. The device based on a molecule of a chiralene according to claim 1, characterized in that, The first graphene dot electrode and the second graphene dot electrode are array electrodes.

4. The device based on a molecule of a chiralene according to claim 3, characterized in that, The first graphene dot electrode and the second graphene dot electrode are nanogap electrodes.

5. A method for the preparation of a device with dual capacitance-inductive function based on a molecule of a buckminsterfullerene, characterized in that, The device for preparing the fulvalene molecule-based capacitive and inductive dual-function device as claimed in any one of claims 1 to 4 comprises the following steps: S100, preparing a metal oxide dielectric layer on a substrate by a thermal evaporation method; S200, preparing a single-layer graphene on a copper foil by a vapor deposition method, and transferring the single-layer graphene to the metal oxide dielectric layer to obtain a graphene dielectric layer; S300, preparing a graphene dot electrode pair on the graphene dielectric layer by an oxygen plasma etching and electrical burnout method; S400, placing the graphene dot electrode pair in a pyridine solution containing a fulvalene molecule and a condensing agent, and allowing the fulvalene molecule to self-assemble with the graphene dot electrode pair to obtain a fulvalene molecule-based capacitive and inductive dual-function device.

6. The method for preparing a device based on a molecule of a chiralene with dual capacitance and inductance functions according to claim 5, characterized in that, In step S100, the metal oxide dielectric layer is selected from an aluminum oxide dielectric layer.

7. The method for preparing a device based on a molecule of a chiralene with dual capacitance and inductance functions according to claim 6, characterized in that, The thickness of the aluminum oxide dielectric layer is 30-40 nm.

8. The method for fabricating a capacitive-inductive dual-function device based on helene molecules as described in claim 5, characterized in that, In step S100, the substrate is selected from a silicon wafer.

9. The method of claim 5, wherein the method further comprises the step of: In step S400, the synthesis route of the fulvalene molecule is as follows: ​ 。 10. The method of claim 5, wherein the method is characterized by: In step S400, the condensing agent is selected from 1-(3-dimethylaminopropyl)-3-2 ethyl carbodiimide hydrochloride.

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