A nanometer thin film based on fullerene molecules and a preparation method thereof
By sintering fullerene precursor films with active metals in an inert atmosphere, the problem of preparing covalently linked fullerene nanofilms in existing technologies has been solved, realizing a simple and stable bottom-up method for preparing nanofilms.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- UNIV OF SCI & TECH OF CHINA
- Filing Date
- 2026-04-01
- Publication Date
- 2026-06-12
AI Technical Summary
Existing technologies struggle to prepare covalently linked fullerene nanofilms from the bottom up using simple and gentle methods, and existing methods typically require high pressure, high temperature, or complex top-down processes.
A method for preparing covalently linked fullerene nanofilms was adopted, which involves sintering fullerene precursor films with active metals in an inert atmosphere and combining this with post-processing steps. This method avoids the use of high-pressure equipment and controls the film thickness and intermolecular covalent bonding by adjusting the sintering parameters.
The bottom-up in-situ controllable preparation of fullerene covalently linked nanofilms was achieved. The process is simple, easy to operate, and produces intact and continuous films without breakage or detachment, with stable intermolecular covalent connections.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of novel carbon material preparation technology, and in particular to a nanofilm based on fullerene molecules and its preparation method. Background Technology
[0002] Fullerenes, as classic zero-dimensional carbon nanomaterials, possess stable molecular structures and unique physicochemical properties, and are often used as basic structural units for constructing novel carbon materials in in-depth research. Currently, the molecules in fullerene molecular crystals can be induced to form covalent bonds between molecules through high temperature and high pressure, ultraviolet irradiation, alkali metal doping, etc., and then assembled into fullerene polymers.
[0003] Among them, the high temperature and high pressure method can prepare one-dimensional orthorhombic, two-dimensional tetragonal, or hexagonal fullerene polymers by controlling temperature and pressure. However, the synthesis conditions of this method are extremely harsh, usually requiring high pressure on the order of GPa and high temperature of about 800℃. Moreover, the structure and properties of the obtained products are not uniform and the controllability is poor. The photopolymerization method of ultraviolet irradiation can usually only obtain fullerene dimers or oligomers, and cannot form continuous two-dimensional film structures. The alkali metal / alkaline earth metal doping method can obtain fullerene polymer-metal atom mixed crystal materials by reacting with fullerene molecules, and then obtain one-dimensional or two-dimensional fullerene polymers through metal removal and exfoliation processes. However, this method belongs to the top-down preparation route, and the obtained products are mostly in the form of dispersions. If two-dimensional fullerene covalently linked films are to be prepared, additional control and assembly are required, and the preparation steps are cumbersome and the process is complicated.
[0004] To date, there is very little research on the bottom-up preparation of covalently linked fullerene films. The industry urgently needs a method that is simple, easy to operate, and operates under mild conditions to prepare covalently linked fullerene nanofilms from the bottom up. Summary of the Invention
[0005] In view of this, this application provides a nanofilm based on fullerene molecules and a method for preparing the same. The preparation method provided by this application does not require high-pressure equipment, is simple in process, convenient in operation, and has mild conditions, and can achieve controllable preparation of the film in situ from the bottom up.
[0006] This application provides a fullerene-based nanofilm, comprising:
[0007] Base;
[0008] A fullerene layer formed on the surface of the substrate; the fullerene layer comprises a single layer or multiple layers of fullerene molecules.
[0009] In some specific implementations, the thickness of the fullerene layer is 1 nm to 200 nm.
[0010] In some specific implementations, adjacent fullerene molecules are linked by covalent bonds.
[0011] In some specific implementations, the fullerene molecule is selected from C 60 C 70 C 78 C 80 C 82 C 84 and C 100 One or more molecules.
[0012] In some specific implementations, the substrate is a copper foil or a silicon wafer with silicon dioxide on its surface.
[0013] Furthermore, this application provides a method for preparing the above-mentioned nanofilm, comprising the following steps:
[0014] Fullerene precursor films and active metals were sintered under sealed conditions in an inert atmosphere, and then post-treated to obtain nanofilms.
[0015] The fullerene precursor film includes a substrate and a fullerene layer precursor formed on the surface of the substrate.
[0016] In some specific implementations, the active metal is selected from one or more of lithium, sodium, potassium, rubidium, cesium, strontium, barium, mercury, bismuth, lead, and zinc.
[0017] In some specific implementations, the sintering temperature is 150℃~1000℃;
[0018] The sintering time is 0.1h to 500h;
[0019] The heating rate for sintering is 1°C·min. -1 ~30℃·min -1 ;
[0020] The inert gas flow rate is 10 sccm to 2000 sccm.
[0021] In some specific implementations, the post-processing specifically involves washing the sintered film sequentially with deionized water and an organic solvent.
[0022] In some specific implementations, the organic solvent is selected from one or more of cyclopentane, cyclohexane, chloroform, carbon tetrachloride, carbon disulfide, benzene, toluene, xylene, trimethylbenzene, and chlorobenzene.
[0023] The washing time for the deionized water is 1 hour to 25 hours;
[0024] The washing time for the organic solvent is 1 hour to 50 hours.
[0025] The fullerene-based nanofilm provided in this application comprises: a substrate and a fullerene layer formed on the surface of the substrate; the fullerene layer comprises a single layer or multiple layers of fullerene molecules. This application deposits fullerene molecules on a substrate to form a single layer or multiple layers of fullerene molecules, resulting in a complete, continuous film without breakage or detachment. Furthermore, the method provided in this application includes: sintering a fullerene precursor film with an active metal under sealed conditions in an inert atmosphere, followed by post-treatment to obtain the nanofilm. The preparation method provided in this application does not require high-pressure equipment, avoiding the harsh high-temperature and high-pressure synthesis conditions of existing technologies. The preparation process is simple, convenient, and the reaction conditions are mild. By adjusting the deposition process and sintering reaction parameters, the thickness, size, and degree of intermolecular covalent bonding of the film can be controlled, achieving bottom-up, in-situ controllable preparation of fullerene covalently linked nanofilms. Attached Figure Description
[0026] Figure 1 An optical photograph of the thin film prepared in Example 1 of this invention;
[0027] Figure 2 The Raman spectrum of the thin film prepared in Example 1 of this invention;
[0028] Figure 3 An optical photograph of the thin film prepared in Example 2 of this invention;
[0029] Figure 4 The image shown is the AFM pattern of the thin film prepared in Example 2 of this invention.
[0030] Figure 5 The Raman spectrum of the thin film prepared in Example 2 of this invention;
[0031] Figure 6 An optical photograph of the thin film prepared in Example 3 of this invention;
[0032] Figure 7 The Raman spectrum of the thin film prepared in Example 3 of this invention;
[0033] Figure 8 An optical photograph of the thin film prepared in Example 4 of this invention;
[0034] Figure 9 The image shows the Raman spectrum of the thin film prepared in Example 4 of this invention. Detailed Implementation
[0035] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.
[0036] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.
[0037] It should be understood that the order of steps or the sequence of actions is not important as long as this application remains operational. Furthermore, two or more steps or actions can be performed simultaneously.
[0038] This application provides a nanofilm based on the covalent linkage of fullerene molecules, comprising:
[0039] Base;
[0040] A fullerene layer formed on the surface of the substrate.
[0041] This application provides a nanofilm based on fullerene molecular covalent bonding, comprising a substrate for supporting the fullerene layer and providing stable structural support for the entire process of nanofilm preparation and subsequent applications. This application does not impose any special limitations on the substrate and can adapt to various planar film-forming substrates, including but not limited to copper foil or silicon wafers with silica coating, preferably planar silicon wafers with silica coating or annealed planar copper foil; the thickness of silica on the silicon wafer surface is 50nm~500nm, preferably 150nm~400nm; the thickness of the copper foil is 10μm~50μm, preferably 20μm~30μm; the dimensions of the substrate are (0.3~5)cm×(0.3~5)cm, preferably (0.5~2)cm×(0.5~2)cm, more preferably 1.0cm×1.0cm.
[0042] The nanofilm provided in this application also includes a fullerene layer, which serves as the core functional layer of the nanofilm and together with the substrate constitutes the nanofilm. In some specific implementations, the thickness of the fullerene layer is 1 nm to 200 nm, preferably 10 nm to 120 nm, and more preferably 20 nm, 30 nm, 40 nm, or 100 nm.
[0043] In some specific implementations, adjacent fullerene molecules within the fullerene layer are stably linked by covalent bonds; wherein the fullerene molecules constituting the fullerene layer exist in the form of fullerene spheroids or amorphous carbon; and the fullerene molecules are selected from C2.60 C 70 C 78 C 80 C 82 C 84 and C 100 One or more of the molecules, preferably C 60 C 70 and C 80 One or more mixtures of the fullerenes; the purity of the fullerene molecules is ≥99.9%.
[0044] Furthermore, this application also provides a method for preparing the above-mentioned nanofilm, comprising the following steps:
[0045] Fullerene precursor films and active metals were sintered under sealed conditions in an inert atmosphere, and then post-treated to obtain nanofilms.
[0046] In this application, the fullerene precursor film includes a substrate and a fullerene layer precursor formed on the surface of the substrate; this application does not specifically limit the source of the fullerene precursor film, but preferably prepares the fullerene precursor film according to the following method:
[0047] Fullerene molecules are deposited onto the surface of a substrate to form a fullerene precursor film. The material and dimensions of the substrate are as described above and will not be repeated here. This application does not specifically limit the deposition method; it can be ultra-high vacuum thermal evaporation or ultrasonic deposition, with ultra-high vacuum thermal evaporation being preferred. In some specific implementations, the ultra-high vacuum thermal evaporation technique involves placing the fullerene raw material in an evaporation source crucible, placing the substrate on the substrate, and depositing the fullerene precursor film under vacuum conditions; the vacuum level is 0.5 × 10⁻⁶. -4 Pa~5×10 -4 Pa, preferably 0.5 × 10 -4 Pa~2×10 -4 Pa, more preferably 0.5 × 10 Pa -4 Pa, 1×10 -4 Pa or 2×10 -4 Pa; the deposition rate is 0.1 Å / s to 10 Å / s, preferably 0.1 Å / s to 1 Å / s, more preferably 0.1 Å / s, 0.3 Å / s, 0.5 Å / s or 1 Å / s.
[0048] This application describes the fullerene precursor film and the active metal being placed together in a reaction vessel under an inert atmosphere. In some specific implementations, the metal is selected from one or more of lithium, sodium, potassium, rubidium, cesium, strontium, barium, mercury, bismuth, lead, and zinc, preferably a mixture of one or more of zinc, lithium, lead, mercury, potassium, bismuth, rubidium, sodium, or strontium; the mass of the metal is 0.5 mg to 1000 mg, preferably 1 mg to 500 mg, more preferably 50 mg, 100 mg, 300 mg, or 500 mg; the inert atmosphere is an argon atmosphere; this application does not specifically limit the reaction vessel, which can be a quartz tube or a ground-glass stoppered quartz vial.
[0049] The reaction vessel of this application can be sealed, either by high-temperature vacuum encapsulation or by encapsulation under inert atmosphere differential pressure; in some specific implementations, the reaction vessel is a quartz tube encapsulated under high-temperature vacuum; the reaction vessel is a ground-glass quartz vial encapsulated under inert atmosphere differential pressure.
[0050] This application describes sintering the aforementioned reaction vessel in an inert atmosphere. The sintering process is not specifically limited, but is preferably carried out in a tube furnace. In some specific implementations, the sintering temperature is 150℃~1000℃, preferably 200℃~900℃, more preferably 400℃, 600℃, 700℃, or 800℃; the sintering time is 0.1h~500h, preferably 1h~100h, more preferably 6h, 10h, 20h, or 50h; and the sintering heating rate is 1℃·min. -1 ~30℃·min -1 Preferably 5℃·min -1 ~25℃·min -1 More preferably 5℃·min -1 10℃·min -1 Or 20℃·min -1 The inert atmosphere is an argon atmosphere; the gas flow rate of the inert atmosphere is 10 sccm to 2000 sccm. In a typical implementation, the specific steps are to place the reaction vessel horizontally in the tube furnace, while ensuring that the reactants in the reaction vessel are in the center of the temperature zone.
[0051] After the gas-solid phase reaction is completed, this application performs post-processing on the sintered film. In some specific implementations, the post-processing specifically involves: removing the reacted nanofilm from the reaction vessel, washing it in two steps with deionized water and an organic solvent, and then drying it after washing.
[0052] In some specific implementations, the organic solvent is selected from one or more of cyclopentane, cyclohexane, chloroform, carbon tetrachloride, carbon disulfide, benzene, toluene, xylene, trimethylbenzene, and chlorobenzene, preferably chloroform, trimethylbenzene, toluene, carbon disulfide, or xylene; the washing time with deionized water is 1h to 25h, preferably 2h to 15h, more preferably 3h, 6h, 10h, or 15h; the washing time with the organic solvent is 1h to 50h, preferably 10h, 30h, 40h, or 50h; the drying temperature is 30℃ to 90℃, preferably 40℃, 60℃, or 80℃; and the drying time is 1h to 20h, preferably 1h, 3h, 10h, or 20h.
[0053] The fullerene-based nanofilm provided in this application comprises: a substrate and a fullerene layer formed on the surface of the substrate; the fullerene layer comprises a single layer or multiple layers of fullerene molecules. This application deposits fullerene molecules on a substrate to form a single layer or multiple layers of fullerene molecules, resulting in a complete, continuous film without breakage or detachment. Furthermore, the method provided in this application includes: sintering a fullerene precursor film with an active metal under sealed conditions in an inert atmosphere, followed by post-treatment to obtain the nanofilm. The preparation method provided in this application does not require high-pressure equipment, avoiding the harsh high-temperature and high-pressure synthesis conditions of existing technologies. The preparation process is simple, convenient, and the reaction conditions are mild. By adjusting the deposition process and sintering reaction parameters, the thickness, size, and degree of intermolecular covalent bonding of the film can be controlled, achieving bottom-up, in-situ controllable preparation of fullerene covalently linked nanofilms.
[0054] The present application is further illustrated below with reference to embodiments. The scope of protection of the present application is not limited to the following embodiments.
[0055] Example 1
[0056] Fullerene C 70 Place a copper foil measuring 0.5cm × 1cm on the substrate inside the evaporation source crucible, close the chamber door, and evacuate to a vacuum level of 2 × 10⁻⁶. -4 At a deposition rate of 1 Å / s, a fullerene precursor film with a thickness of 100 nm was obtained. 100 mg of zinc, lithium (molar ratio 4:1), and the fullerene precursor film were added to a 15 mm diameter, partially sealed quartz tube in an argon-atmospheric glove box, followed by high-temperature vacuum sealing. The quartz tube containing the reactants was then placed in the central temperature zone of a tube furnace, and the heating rate was set to 20 °C / min. −1 The reaction was carried out at 700℃ for 6 hours. After the heated quartz tube was removed and cooled to room temperature, the film was removed from the quartz tube and washed with deionized water for 6 hours, followed by washing with organic solvents such as chloroform and trimethylbenzene for 30 hours. After drying at 40℃ for 3 hours, a clean film based on fullerene molecules C was obtained.70 Covalently linked nanofilms.
[0057] Figure 1 The image shows an optical photograph of the thin film prepared in Example 1 of the present invention, which clearly demonstrates that the obtained thin film completely covers the substrate surface, without pores, cracks, or peeling, and presents a continuous and uniform overall film structure. Figure 2 The image shows the Raman spectrum of the thin film prepared in Example 1 of this invention. The characteristic peaks at 1464 cm⁻¹ and 1579 cm⁻¹ indicate that the transformation from van der Waals forces to covalent bonds between fullerene molecules was achieved after the gas-solid reaction, and the film remained stable after a second washing.
[0058] Example 2
[0059] Fullerene C 60 and fullerene C 80 Place a 0.5cm × 1cm copper foil inside the evaporation source crucible, place it on the substrate, close the chamber door, and evacuate to a vacuum level of 0.5 × 10⁻⁶. -4 At a deposition rate of 0.1 Å / s, a fullerene precursor film with a thickness of 20 nm was obtained. 300 mg of metallic lead, mercury, and potassium (molar ratio 1:1:1) and the fullerene precursor film were added to a ground-glass stoppered quartz vial in an argon-atmosphere glove box, and the vial was sealed tightly under an argon atmosphere. The vial containing the reactants was placed in the center temperature zone of a tube furnace, with an argon flow rate and a heating rate set at 10 °C / min. −1 The reaction was carried out at 800℃ for 20 h. After the heated ground-glass stoppered quartz vial was removed and cooled to room temperature, the film was removed from the vial and washed with deionized water for 10 h, then washed with organic solvents such as toluene and carbon disulfide for 50 h. After drying at 60℃ for 10 h, a clean film based on fullerene molecules C was obtained. 60 and C 80 Covalently linked nanofilms.
[0060] Figure 3 The optical photographs of the thin films prepared in Example 2 of the present invention show the macroscopic morphology of the 20nm ultrathin films. The films are continuous and complete on the silicon substrate, without any defects visible to the naked eye, and uniformly cover the substrate surface, proving that the present invention can achieve the controllable preparation of ultrathin nanofilms. Figure 4 The image shown is the AFM pattern of the thin film prepared in Example 2 of this invention, which proves that the thin film also has excellent uniformity and flatness at the microscopic level. Figure 5 The image shows the Raman spectrum of the thin film prepared in Example 2 of this invention. The characteristic peaks at 1464 cm⁻¹ and 1580 cm⁻¹ indicate that the gas-solid reaction achieved the transformation from van der Waals forces to covalent bonds between fullerene molecules, and the film remained stable after a second washing.
[0061] Example 3
[0062] Fullerene C 70 and fullerene C 80 Place a copper foil measuring 0.5cm × 1cm on the substrate inside the evaporation source crucible, close the chamber door, and evacuate to a vacuum level of 1 × 10⁻⁶. -4 At a deposition rate of 0.5 Å / s, a fullerene precursor film with a thickness of 20 nm was obtained. 500 mg of bismuth, rubidium, sodium, and strontium (molar ratio 2:2:3:3) and the fullerene precursor film were added to a ground-glass stoppered quartz vial in an argon-atmosphere glove box, and the vial was sealed tightly under argon atmosphere. The vial containing the reactants was placed in the central temperature zone of a tube furnace, and the heating rate was set to 5 °C / min. −1 The reaction was carried out at 600℃ for 50 h. After the heated ground-glass stoppered quartz vial was removed and cooled to room temperature, the film was removed from the vial and washed with deionized water for 15 h, then washed with organic solvents such as p-xylene and chlorobenzene for 40 h. After drying at 80℃ for 20 h, a clean film based on fullerene molecules C was obtained. 70 and C 80 Covalently linked nanofilms.
[0063] Figure 6 The optical photographs of the thin films prepared in Example 3 of this invention show the macroscopic morphology of the 40 nm thick films. The films are continuous, uniform, and completely cover the substrate without defects or detachment, proving that the present invention can prepare structurally complete covalently linked fullerene films under different reaction temperatures, reaction times, and active metal systems. Figure 7 The image shows the Raman spectrum of the thin film prepared in Example 3 of this invention. The characteristic peaks at 1464 cm⁻¹ and 1595 cm⁻¹ indicate that the gas-solid reaction achieved the transformation from van der Waals forces to covalent bonds between fullerene molecules, and the film remained stable after a second washing.
[0064] Example 4
[0065] Fullerene C 60 Place a copper foil measuring 0.5cm × 1cm on the substrate inside the evaporation source crucible, close the chamber door, and evacuate to a vacuum level of 1 × 10⁻⁶. -4 A fullerene precursor film with a thickness of 20 nm was deposited at a deposition rate of 0.3 Å / s. 50 mg of potassium metal and the fullerene precursor film were added to a 15 mm diameter, sealed quartz tube in an argon-atmospheric glove box, followed by high-temperature vacuum sealing. The quartz tube containing the reactants was then placed in the central temperature zone of a tube furnace, and the heating rate was set to 5 °C / min. −1The reaction was carried out at 400℃ for 10 hours. After the heated quartz tube was removed and cooled to room temperature, the film was removed from the quartz tube and washed with deionized water for 3 hours, followed by washing with organic solvents such as chloroform and thiobenzene for 10 hours. After drying at 60℃ for 1 hour, a clean film based on fullerene molecules C was obtained. 60 Covalently linked nanofilms.
[0066] Figure 8 The image shows an optical photograph of the thin film prepared in Example 4 of this invention, which demonstrates the macroscopic morphology of the thin film prepared under a single alkali metal system and low-temperature reaction conditions. The film is intact and continuous without any breakage or detachment, proving that this invention can still successfully prepare structurally intact fullerene covalently linked thin films under a single active metal and a relatively mild reaction temperature. Figure 9 The image shows the Raman spectrum of the thin film prepared in Example 4 of this invention. The characteristic peaks at 1464 cm⁻¹ and 1587 cm⁻¹ indicate that the single C₂ after the gas-solid reaction... 60 Intermolecular covalent bonds were successfully formed between fullerene molecules.
[0067] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in this application, based on the technical solution and application concept of this application, should be included within the scope of protection of this application.
Claims
1. A nanofilm based on fullerene molecules, characterized in that, include: Base; A fullerene layer formed on the surface of the substrate; the fullerene layer comprises a single layer or multiple layers of fullerene molecules.
2. The nanofilm according to claim 1, characterized in that, The thickness of the fullerene layer is 1 nm to 200 nm.
3. The nanofilm according to claim 1, characterized in that, Adjacent fullerene molecules are linked by covalent bonds.
4. The nanofilm according to any one of claims 1 to 3, characterized in that, The fullerene molecule is selected from C 60 C 70 C 78 C 80 C 82 C 84 and C 100 One or more molecules.
5. The nanofilm according to claim 1, characterized in that, The substrate is a copper foil or a silicon wafer with silicon dioxide on its surface.
6. A method for preparing a nanofilm as described in any one of claims 1 to 5, characterized in that, Includes the following steps: Fullerene precursor films and active metals were sintered under sealed conditions in an inert atmosphere, and then post-treated to obtain nanofilms. The fullerene precursor film includes a substrate and a fullerene layer precursor formed on the surface of the substrate.
7. The preparation method according to claim 6, characterized in that, The active metal is selected from one or more of lithium, sodium, potassium, rubidium, cesium, strontium, barium, mercury, bismuth, lead, and zinc.
8. The preparation method according to claim 6, characterized in that, The sintering temperature is 150℃~1000℃; The sintering time is 0.1h to 500h; The heating rate for sintering is 1°C·min. -1 ~30℃·min -1 ; The inert gas flow rate is 10 sccm to 2000 sccm.
9. The preparation method according to any one of claims 6 to 8, characterized in that, The post-processing specifically involves washing the sintered film with deionized water and an organic solvent in sequence.
10. The preparation method according to claim 9, characterized in that, The organic solvent is selected from one or more of cyclopentane, cyclohexane, chloroform, carbon tetrachloride, carbon disulfide, benzene, toluene, xylene, trimethylbenzene, and chlorobenzene; The washing time for the deionized water is 1 hour to 25 hours; The washing time for the organic solvent is 1 hour to 50 hours.