WO2025007376A1 - 一种富勒烯单晶薄膜及其制备方法和用途 - Google Patents

一种富勒烯单晶薄膜及其制备方法和用途 Download PDF

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WO2025007376A1
WO2025007376A1 PCT/CN2023/109278 CN2023109278W WO2025007376A1 WO 2025007376 A1 WO2025007376 A1 WO 2025007376A1 CN 2023109278 W CN2023109278 W CN 2023109278W WO 2025007376 A1 WO2025007376 A1 WO 2025007376A1
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fullerene
single crystal
organic
substrate
thin film
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French (fr)
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李寒莹
赵裕杰
彭博宇
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Zhejiang University
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Zhejiang University
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Priority to US18/873,715 priority patent/US20260103820A1/en
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    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/005—Epitaxial layer growth
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    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
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    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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    • H10K71/191—Deposition of organic active material characterised by provisions for the orientation or alignment of the layer to be deposited
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the technical field of organic semiconductors, and in particular to a fullerene single crystal film and a preparation method and application thereof.
  • fullerene As a star material in the field of optoelectronics, fullerene has broad application prospects in many fields of organic electronics, such as organic solar cells, organic field effect transistors, organic light-emitting diodes, organic photodetectors, etc. So far, these applications of fullerene have been verified in the laboratory stage. However, fullerene has not yet been industrialized in the field of optoelectronics. This is mainly because the current method for preparing fullerene films is usually evaporation. The evaporation method requires high temperature (>400°C), high vacuum and harsh conditions and requires expensive equipment (ACS Nano 2013, 7, 10, 9122-9128).
  • fullerene film obtained by evaporation has a higher defect state density than the fullerene crystal, which has an adverse effect on its optoelectronic properties such as electron mobility and exciton diffusion distance.
  • fullerene crystals by low-cost solution method.
  • fullerene is more difficult to control its crystallization process due to its unique zero-dimensional configuration. This is mainly manifested in the following two points: on the one hand, the contact area between fullerene molecules is much smaller than that of planar molecules, resulting in a weaker driving force for crystallization; on the other hand, due to the zero-dimensional characteristics of fullerene molecules, it is easy to rotate and has no advantageous orientation.
  • Traditional methods for preparing fullerene crystals include liquid-liquid interface precipitation method (Small 2018, 14, 11, e1703624.), supramolecular gel crystallization method (Adv. Sci.
  • liquid-liquid interface precipitation method which uses the slow mixing of solvents at the interface of fullerene's good solvent and poor solvent to make fullerene supersaturated at the interface, thereby promoting the nucleation and growth of crystals.
  • this method has received extensive attention and research, it has some serious defects, such as the uncontrollable nucleation and growth process of the crystal, which leads to poor experimental repeatability and chaotic size distribution of fullerene crystals.
  • the liquid-liquid interface precipitation method is a non-in-situ growth process, which requires a complex transfer process for optoelectronic applications of the crystal. The transfer process inevitably damages the crystal and makes the miniaturization and integration of the device difficult.
  • Hexagonal crystals can be obtained in pseudo-three-dimensional solvents such as carbon tetrachloride, while one-dimensional needle-shaped crystals are obtained in pseudo-two-dimensional benzene solvents substituted at the meta position. Therefore, for the preparation of fullerene single crystal thin films by the solution method, the selection and regulation of the solvent are crucial. In order to obtain a fullerene single crystal thin film with high coverage and good orientation, it is very advantageous to control the morphology of the fullerene crystal into a strip shape through solvent engineering.
  • fullerene film is a large-area single crystal film prepared in situ by a solution method, with high coverage, uniform orientation, high uniformity and continuous preparation.
  • the existing technology cannot prepare the above-mentioned ideal fullerene single crystal film.
  • fullerene crystal films are greatly dependent on the choice of solvents. How to use solvent engineering to obtain fullerene single crystal films with good orientation and high coverage as much as possible is still a mystery. Therefore, the in-situ preparation of ideal large-area fullerene single crystal films by a solution method is still a huge technical problem, and it is also a prerequisite for the integration and industrialization of fullerene optoelectronic devices.
  • the object of the present invention is to provide a fullerene single crystal film and a preparation method and use thereof.
  • the first aspect of the present invention protects a method for preparing a fullerene single crystal thin film using a gas-liquid-solid three-phase interface, comprising the following steps:
  • the fullerene is selected from one or more of C60, C70, C76, C78, C80 and C84.
  • the fullerene is selected from one or both of C60 and C70.
  • the selected solvent is selected from one or more of o-xylene, 2-methylthiophene, 2-chlorothiophene, 2-chlorofuran, 3-methylthiophene, 2-ethylthiophene, m-xylene, m-difluorobenzene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, tetralin, 1-methylnaphthalene, carbon disulfide, 1,1,2,2-tetrachloroethane, carbon tetrachloride, 2-methoxythiophene, phenethyl ether, 2-chloro-3-methylthiophene and 2,5-dichlorothiophene.
  • the concentration of the fullerene is 0.2 to 20 mg/mL.
  • it is 0.4 mg/mL to 10 mg/mL.
  • the material of the substrate is selected from one or more of silicon, indium tin oxide, glass, quartz, sapphire, polyimide and polyethylene terephthalate.
  • a wetting layer is provided on the substrate.
  • the material of the wetting layer is selected from one or more of benzocyclobutene, polyvinyl alcohol, cross-linked polymethyl methacrylate, cross-linked polystyrene, aluminum oxide, titanium oxide, zinc oxide, ethoxylated polyethyleneimine, phenyltrichlorosilane, gold and aluminum.
  • the solution shearing method is to set a shearing tool on the substrate so that the mixed solution is located between the shearing tool and the substrate, and the substrate or the shearing tool is operated at a certain linear speed.
  • the shearing tool is selected from one or more of a stainless steel polished rod, a stainless steel wire rod, a polytetrafluoroethylene rod, a scraper and a coating head.
  • the distance between the shearing tool and the substrate is 20 ⁇ m to 400 ⁇ m.
  • the distance between the shearing tool and the substrate is 50 ⁇ m to 200 ⁇ m.
  • the linear velocity in the solution shearing method is 1 ⁇ m/s to 1 mm/s.
  • the linear velocity in the solution shearing method is 5 ⁇ m/s to 200 ⁇ m/s.
  • the temperature of crystal growth is 20°C to 120°C.
  • the temperature of the crystal growth is 25°C to 60°C.
  • the second aspect of the present invention protects the fullerene single crystal thin film obtained by the preparation method as described above.
  • the third aspect of the present invention protects the use of the fullerene single crystal thin film as described above in the preparation of optoelectronic devices.
  • a fourth aspect of the present invention protects an optoelectronic device comprising the fullerene single crystal thin film as described above.
  • the optoelectronic device is selected from one or more of an organic field effect transistor, an organic solar cell, an organic complementary inverter, an organic circuit, an organic light emitting diode, an organic memory storage device, an organic photodetector and an organic thermoelectric device.
  • the present invention has the following beneficial effects:
  • the present invention directly controls the nucleation density of fullerene at the three-phase line and utilizes the continuous movement of the three-phase line to prepare a large-area fullerene single crystal film.
  • the morphology of the fullerene crystal is controlled by controlling the solvent to obtain a large-area fullerene single crystal film with uniform orientation, high uniformity and high coverage.
  • the large-area fullerene single crystal film has the highest coverage currently (greater than 95%).
  • the high-quality fullerene single crystal film of the present invention can realize the practical application of fullerene in many fields of organic electronics.
  • the coefficient of variation of the mobility and threshold voltage of the organic field-effect transistors (OFETs) array based on the C60 fullerene single crystal film is less than 15%, which is the most uniform performance value among the OFETs currently prepared based on the C60 fullerene single crystal film;
  • the organic field-effect transistor based on the C70 fullerene single crystal film can achieve a mobility of 0.195cm2V - 1s -1 , which is the highest mobility among the OFETs currently prepared based on the C70 fullerene single crystal.
  • Other applications such as organic solar cells, organic complementary inverters, etc. also show excellent performance.
  • FIG. 1 shows an overall and partially magnified optical microscope image of the C60 fullerene single crystal film prepared in Example 1 of the present application.
  • FIG. 2 shows an optical microscope photograph of the C60 fullerene single crystal film prepared in Example 2 of the present application.
  • FIG. 3 shows an optical microscope photograph of the C60 fullerene single crystal film prepared in Example 3 of the present application.
  • FIG. 4 shows an optical microscope photograph of the C60 fullerene single crystal film prepared in Example 4 of the present application.
  • FIG. 5 shows an optical microscope photograph of the C60 fullerene single crystal film prepared in Example 5 of the present application.
  • FIG. 6 shows an optical microscope photograph of the C60 fullerene single crystal film prepared in Example 6 of the present application.
  • FIG. 7 shows an optical microscope photograph of the C60 fullerene single crystal film prepared in Example 7 of the present application.
  • FIG8 shows an overall and partially magnified optical microscope image of the C70 fullerene single crystal film obtained in Example 8 of the present application.
  • FIG. 9 shows an optical microscope photograph of the C70 fullerene single crystal film prepared in Example 9 of the present application.
  • Figure 10 shows the characterization of the field effect transistor array prepared using the C60 fullerene single crystal thin film in Example 10 of the present application.
  • (a) and (b) are the transfer characteristic curves and typical output characteristic curves of 70 devices, respectively, where the illustration in (a) is a schematic diagram of the structure of the organic field effect transistor;
  • (c) and (d) are the mobility and threshold voltage statistics of the 70 devices, respectively.
  • FIG. 11 shows a typical transfer characteristic curve and an output characteristic curve of a field effect transistor prepared using a C70 fullerene single crystal thin film in Example 11 of the present application.
  • Figure 12 shows the structural schematic diagram and J-V curve of the organic solar cell made based on C60 fullerene single crystal thin film in Example 12 of the present application. Among them, (a) is the structural schematic diagram, and (b) is the J-V curve.
  • Figure 13 shows an optical microscope image and performance curve of an organic complementary inverter made based on a C60 fullerene single crystal thin film in Example 13 of the present application.
  • (a) is an optical microscope image
  • (b) is a voltage conversion curve
  • the inset is a circuit diagram of the organic complementary inverter
  • (c) is a voltage gain curve.
  • FIG. 14 shows an optical microscope photograph of the film prepared in Comparative Example 1 of the present application.
  • FIG. 15 shows an optical microscope photograph of the film prepared in Comparative Example 2 of the present application.
  • FIG. 16 shows an optical microscope photograph of the film prepared in Comparative Example 3 of the present application.
  • FIG. 17 shows an optical microscope photograph of the film prepared in Comparative Example 4 of the present application.
  • the fullerene film prepared by the prior art has the disadvantages of low crystallinity, small area, disordered orientation, low coverage, poor uniformity, etc. After extensive research, it was found that the solution shearing method can make fullerene grow on the substrate surface. Through the regulation of solvent engineering and crystal nucleation growth behavior at the air-solution-substrate three-phase line, a high-quality large-area fullerene single crystal film was successfully prepared, which has high coverage, uniform orientation, high crystallinity, and good uniformity.
  • the fullerene single crystal film of the present invention meets the application requirements of fullerene materials in the optoelectronic field, and can be applied to the fields of organic field effect transistors, organic solar cells, organic circuits, etc.
  • the first aspect of the present invention protects a method for preparing a fullerene single crystal thin film using a gas-liquid-solid three-phase interface, comprising the following steps:
  • the method of the present invention does not require additional fixtures or photoresist arrays to assist crystallization.
  • the evaporation of the solvent at the triple phase line promotes crystal nucleation and the continuous movement of the triple phase line promotes the continuous growth of oriented fullerene crystals, thereby obtaining a large-area fullerene single crystal film with high coverage and scalable preparation.
  • the fullerene is selected from one or more of C60, C70, C76, C78, C80 and C84. Preferably, it is C60 or C70.
  • the selected solvent is selected from one or more of o-xylene, 2-methylthiophene, 2-chlorothiophene, 2-chlorofuran, 3-methylthiophene, 2-ethylthiophene, m-xylene, m-difluorobenzene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, tetralin, 1-methylnaphthalene, carbon disulfide, 1,1,2,2-tetrachloroethane, carbon tetrachloride, 2-methoxythiophene, phenethyl ether, 2-chloro-3-methylthiophene and 2,5-dichlorothiophene.
  • the solvent can be a single solvent, such as 2-chlorothiophene, 2-chloro-3-methylthiophene, 2-methoxythiophene, 3-methylthiophene, 2-ethylthiophene and o-xylene.
  • Fullerene crystals are very easy to couple with solvent molecules inside the crystals to form solvated crystals. Therefore, fullerene crystals often present different morphologies in different solvents. For example, C60 fullerene usually presents needle-shaped crystals in the solvent meta-xylene, and usually presents hexagonal crystals in the solvent carbon tetrachloride.
  • the present invention selects solvents that can obtain ribbon crystals with good orientation and high coverage as much as possible.
  • a second solvent can be added to regulate the crystal morphology.
  • C60 fullerene crystals present hexagonal crystals with no orientation, discontinuity and low coverage in carbon tetrachloride.
  • Solvents that can form needle-shaped crystals such as meta-xylene, 3-methylthiophene, toluene, etc. can be added to combine the two morphological features to form strip-shaped crystals with good orientation and high coverage.
  • the two solvents can increase the coverage of fullerene single crystal film by at least 8 times.
  • the solvent may be a mixture of two or more solvents, such as 3-methylthiophene and carbon tetrachloride, 2-chlorothiophene and m-xylene, 2-chlorothiophene and 2-methylthiophene.
  • the volume ratio of 3-methylthiophene to carbon tetrachloride is 1:(1-5), or 1:(1-2.5), 1:(2-4.2), 1:(3.6-5), specifically 1:3;
  • the volume ratio of 2-chlorothiophene to m-xylene is (1-6):1, or (1-3):1, (1.5-4.6):1, (3.6-5.8):1, (4.2-6):1, specifically it can be 4:1;
  • the solvent is a mixture of 2-chlorothiophene and m-xylene, the volume ratio of 2-chlorothiophene and m-xylene is (1-15):1, it can also be (1-4.2):1, (3.4-5.6):1, (4.8-10.3):1, (8.6-15):1, specifically it can be 9:1.
  • the concentration of the fullerene is 0.2-20 mg/mL, for example, 0.4-2.2 mg/mL, 2.8-3.2 mg/mL, 2.9-4.6 mg/mL, 3.6-6.1 mg/mL, 5.7-7.2 mg/mL, 6.9-9.2 mg/mL, 8.3-10 mg/mL, 0.4-10 mg/mL. In some specific embodiments, 0.45 mg/mL, 3 mg/mL, 6 mg/mL, 7.5 mg/mL, 9 mg/mL, 10 mg/mL.
  • the material of the substrate is selected from silicon, indium tin oxide, glass, quartz, sapphire, One or more of polyimide and polyethylene terephthalate.
  • silicon, indium tin oxide (ITO) for example, the substrate is a silicon wafer heavily doped with phosphorus or boron. In a specific embodiment, it is a heavily doped phosphorus silicon wafer with a layer of silicon dioxide with a thickness of 285nm on the surface.
  • a wetting layer is provided on the substrate.
  • the material of the wetting layer is selected from benzocyclobutene (BCB), polyvinyl alcohol (PVA), cross-linked polymethyl methacrylate (c-PMMA), cross-linked polystyrene (c-PS), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), zinc oxide (ZnO), ethoxylated polyethyleneimine (PEIE), phenyltrichlorosilane (PTS), gold (Au), aluminum (Al), etc.
  • BCB benzocyclobutene
  • PVA polyvinyl alcohol
  • c-PMMA cross-linked polymethyl methacrylate
  • c-PS cross-linked polystyrene
  • Al 2 O 3 aluminum oxide
  • TiO 2 titanium oxide
  • ZnO zinc oxide
  • ZnO zinc oxide
  • PEIE ethoxylated polyethyleneimine
  • PTS phenyltrichlorosilane
  • gold Au
  • the preparation method of the wetting layer can be spin coating (polymer), evaporation (metal), sol-gel (metal oxide), gas phase method (self-assembled monolayer), such as when the material is a polymer, such as PVA, c-PMMA, c-PS, the spin coating method is used; when the material is a metal, such as Au, Al, the evaporation method is used; when the material is a metal oxide, such as Al 2 O 3 , TiO 2 , ZnO, the sol-gel method is used; when the material is a self-assembled monolayer, such as PTS, the gas phase method is used.
  • the material of the wetting layer is BCB, c-PMMA, Au, PEIE, PTS.
  • the solution shearing method is to set a shearing tool on the substrate so that the mixed solution is located between the shearing tool and the substrate, and the substrate or the shearing tool is operated at a certain linear speed, preferably the substrate is operated at a certain linear speed, and a large-area fullerene single crystal film with high coverage is obtained on the substrate after the operation.
  • the shearing tool is selected from one or more of a stainless steel light rod, a stainless steel wire rod, a polytetrafluoroethylene rod, a scraper and a coating head. In a specific embodiment, it is a stainless steel light rod.
  • the spacing between the shearing tool and the substrate is 20 ⁇ m to 400 ⁇ m, for example, 50 ⁇ m to 150 ⁇ m, 100 ⁇ m to 250 ⁇ m, 200 ⁇ m to 350 ⁇ m, 300 ⁇ m to 400 ⁇ m, 50 ⁇ m to 200 ⁇ m, 100 ⁇ m.
  • the linear velocity in the solution shearing method is 1 ⁇ m/s to 1 mm/s, for example, 5 ⁇ m/s to 105 ⁇ m/s, 58 ⁇ m/s to 155 ⁇ m/s, 126 ⁇ m/s to 205 ⁇ m/s, 189 ⁇ m/s to 450 ⁇ m/s, 350 ⁇ m/s to 600 ⁇ m/s, 550 ⁇ m/s to 780 ⁇ m/s, 700 ⁇ m/s to 950 ⁇ m/s, 820 ⁇ m/s to 1 mm/s, 8 ⁇ m/s, 10 ⁇ m/s, 12 ⁇ m/s, 15 ⁇ m/s, or 20 ⁇ m/s.
  • the temperature of the crystal growth is 20°C to 120°C, for example, 20°C to 45°C, 36°C to 58°C, 47°C to 78°C, 62°C to 96°C, 84°C to 105°C, 96°C to 120°C, 25°C to 60°C. In some specific embodiments, it is 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C. Due to the difficulty of fullerene crystal growth, it is necessary to finely control the growth conditions such as substrate temperature, shear rate, solution concentration, etc. to control the nucleation and growth process of the crystal.
  • the solvent evaporates too quickly, the nucleation density at the gas-liquid-solid triple line is too high, and there is enough solute in all directions for the crystal nucleus to grow, resulting in disordered orientation of the fullerene crystal and deterioration of the morphology, such as increased roughness.
  • the line speed can be increased and the concentration of the mixed liquid can be reduced.
  • the temperature is too low, the solvent evaporates too slowly, making nucleation at the triple line difficult, and only some disordered amorphous can be formed. At this time, the line speed can be reduced and the concentration of the mixed liquid can be increased.
  • the second aspect of the present invention protects the fullerene single crystal film obtained by the preparation method described above.
  • the coverage of the fullerene single crystal film on the substrate can be as high as 90% or more.
  • the coverage is obtained by analyzing the fullerene single crystal film with ImageJ software after observing it with an optical microscope.
  • the third aspect of the present invention protects the use of the fullerene single crystal film as described above in the preparation of optoelectronic devices.
  • a fourth aspect of the present invention protects a photoelectric device, comprising the fullerene single crystal thin film as described above.
  • the optoelectronic device is selected from one or more of an organic field effect transistor, an organic solar cell, an organic complementary inverter, an organic circuit, an organic light emitting diode, an organic memory storage device, an organic photodetector and an organic thermoelectric device.
  • the preparation method of the organic field effect transistor is as follows:
  • the source-drain electrode is a general term for the source (Source, S) and the drain (Drain, D).
  • the voltage and current between the source and the drain are represented by V DS and I DS respectively.
  • the source-drain electrode is prepared by one or more methods selected from the group consisting of evaporation, transfer and printing.
  • the source-drain electrode is selected from one or more of silver, lithium fluoride/aluminum, gold, graphene, calcium and magnesium.
  • the preparation method of the organic solar cell is as follows:
  • the material of the donor material layer is selected from donor small molecules and donor polymers. More preferably, the donor small molecule is selected from 2-((7-(4-(dimethylphenylamino)phenyl)benzo[C][1,2,5]thiadiazol-4-yl)methylene)malononitrile (DTDCPB), and the donor polymer is selected from poly(3-hexylthiophene-2,5-diyl) (P3HT).
  • the donor small molecule is selected from 2-((7-(4-(dimethylphenylamino)phenyl)benzo[C][1,2,5]thiadiazol-4-yl)methylene)malononitrile (DTDCPB)
  • the donor polymer is selected from poly(3-hexylthiophene-2,5-diyl) (P3HT).
  • the preparation method of the donor material layer is selected from one or both of spin coating and evaporation.
  • the top electrode is selected from gold, molybdenum trioxide/silver, platinum, titanium, chromium, etc.
  • the preparation method of the top electrode is selected from one or more of an evaporation method, a transfer method and a printing method.
  • the preparation method of the organic complementary inverter is as follows:
  • a p-type semiconductor thin film is grown on the other side of the substrate of the fullerene single crystal thin film as described above.
  • the growth method of the p-type semiconductor film is selected from one or more of a solution shearing method, a droplet fixed crystallization method, an evaporation method and a physical vapor transport method.
  • the material of the p-type semiconductor film is selected from one or more of heterocyclic and benzoheterocyclic derivatives, acene compounds and their derivatives, oligothiophene derivatives and porphyrin derivatives.
  • the electrode is selected from one or more of silver and gold.
  • the coverage of the fullerene single crystal film obtained by the method of the present invention is greater than 95%, and has the advantages of large area, high uniformity and uniform orientation.
  • the organic field effect transistor array obtained by using the C60 fullerene single crystal film of the present invention has good electron transmission performance, the highest electron mobility of the organic field effect transistor array exceeds 1cm 2 V -1 s -1 , and the coefficient of variation of the electron mobility is only 13.3%, which is much lower than 42.9% reported in the existing literature; the organic field effect transistor array obtained by using the C70 single crystal film can achieve an electron mobility of 0.195cm 2 V -1 s -1 , which is much higher than 0.0132cm 2 V -1 s -1 reported in the existing literature.
  • the organic solar cell obtained by using the C60 fullerene single crystal film of the present invention exhibits a good photovoltaic effect, and the photoelectric conversion efficiency can reach 0.123%.
  • the organic complementary inverter obtained by using the fullerene single crystal film of the present invention has almost no voltage loss and high voltage gain.
  • the fullerene single crystal film obtained by the method of the present invention has practical application potential in the field of optoelectronics and complementary circuit integration.
  • a large-area fullerene single crystal thin film is prepared with reference to the materials and parameters in Table 1.
  • the preparation method includes the following steps:
  • the wetting layer is made of polymer such as BCB, c-PMMA, PEIE, spin coating is used; when the wetting layer is made of polymer such as BCB, c-PMMA, PEIE, spin coating is used;
  • the material of the layer is Au, the evaporation method is used; when the material of the wetting layer is PTS, the vapor phase method is used.
  • the silicon wafer is a P-type highly doped silicon wafer with a layer of silicon dioxide with a thickness of 285nm on the surface.
  • a large area of fullerene single crystal thin film can be obtained by the method of the present application; as shown in FIG. 1b, in the C60 fullerene single crystal thin film obtained in Example 1, each crystal has the same orientation and similar color, and the crystal has no obvious morphological defects such as cracks, voids, dendritic morphology, etc., indicating that the method of the present application can obtain a high-quality fullerene single crystal thin film with uniform orientation and high uniformity. Furthermore, the coverage of the single crystal thin film was analyzed by ImageJ software, and as shown in FIG. 1b, the crystal coverage was as high as 84%.
  • each crystal of the C60 fullerene and C70 fullerene single crystal films obtained by the method of the present application has similar orientation and color, and the highest coverage can be greater than 95%, that is, a fullerene single crystal film with uniform orientation, high uniformity and high coverage is obtained.
  • the C60 fullerene single crystal thin film obtained in embodiment 1 is used to prepare an organic field effect transistor array, including the following steps:
  • Source and drain electrodes are evaporated on the C60 fullerene single crystal film obtained in Example 1, that is, the mask is fixed on the C60 fullerene single crystal film, 1nm LiF and 80nm Al are sequentially evaporated as source and drain electrodes, and the highly doped silicon and silicon dioxide/BCB of the substrate are used as the gate electrode and the gate insulating layer respectively to obtain an organic field effect transistor array.
  • the N-type transfer characteristic curves (gate voltage V G :-10 ⁇ 40V; source-drain voltage V DS :40V) and output characteristic curves (gate voltage V G :0 ⁇ 40V, step is 8V; source-drain voltage V DS :0 ⁇ 40V) of 70 organic field effect transistors were measured in a glove box using a semiconductor parameter analyzer.
  • Example 11 an organic field effect transistor is prepared based on the C70 fullerene single crystal thin film of Example 8. The process includes the following:
  • the basic process is the same as 10, the difference is that the evaporated source and drain electrodes are Ag, and the rest are the same.
  • the N-type transfer characteristic curve (V G : -10 ⁇ 50V; V DS : 50V) and output characteristic curve (V G : 0 ⁇ 50V, step is 10V; V DS : 0 ⁇ 50V) of the organic field effect transistor were measured using a semiconductor parameter analyzer in a glove box. The results are shown in FIG11 .
  • the on-off ratio (I on /I off ) is an important performance indicator of an organic field effect transistor, indicating the current ratio of the organic field effect transistor in the on state and the off state. The larger the on-off ratio, the better the performance of the organic field effect transistor.
  • the electron mobility of the organic field effect transistor based on C70 fullerene single crystal film is as high as 0.195cm2V - 1s -1 , which is the highest value of OFETs based on C70 fullerene single crystal.
  • the highest electron mobility of C70 fullerene single crystal is only 0.0132cm2V - 1s - 1 (Chemical Physics Letters.2022,807,140094).
  • Example 12 an organic solar cell is prepared based on the C60 fullerene single crystal film of Example 7.
  • the process includes the following:
  • a layer of DTDCPB with a thickness of 60 nm was prepared on the C60 fullerene single crystal film of Example 7 by evaporation to form a double-layer structure film.
  • step 2) The organic solar cell obtained in step 2) was irradiated with a solar simulator in a glove box, and a current density-voltage (J-V) curve was obtained with a semiconductor parameter analyzer.
  • the open circuit voltage (Voc), short circuit current (Jsc), fill factor (FF) and photoelectric conversion efficiency (PCE) were obtained based on the J-V curve. The results are shown in Figure 12.
  • Open circuit voltage refers to the voltage generated by the device after illumination when there is no current loop (positive and negative electrodes are open circuit), that is, the maximum output voltage of the solar cell, the unit is V; short circuit current (Jsc) refers to the current that can be generated by the illuminated device when the external electric field is zero when the circuit is formed (positive and negative electrodes are short-circuited), that is, the maximum output current of the solar cell; the unit is A/ cm2 or mA/ cm2 .
  • Fill factor is the ratio of the product of current and voltage when the battery has maximum output power to the product of short circuit current and open circuit voltage.
  • Power conversion efficiency refers to the efficiency of solar cells in converting solar energy into electrical energy.
  • the organic solar cell made based on the high coverage fullerene single crystal film of the present application exhibits a good photovoltaic effect, and the photoelectric conversion efficiency can reach 0.123%, indicating that the fullerene single crystal film has practical application potential in the optoelectronic field.
  • Example 13 an organic complementary inverter is prepared based on the C60 fullerene single crystal thin film of Example 1.
  • a single crystal film of 1,4,8,11-tetramethyl-6,13-(triethylsilylethynyl)pentacene (TMTES-PEN) was grown on the other side of the substrate containing the C60 fullerene single crystal film of Example 1.
  • the growth method was the same as that of the substrate containing the C60 fullerene single crystal film of Example 1.
  • the same solution shearing method was used for the preparation of the polyene single crystal film, except that the concentration of the mixed solution formed by the solvent and TMTES-PEN, the substrate temperature, and the shear rate were m-xylene, 8 mg/mL, 40°C, and 50 ⁇ m/s, respectively.
  • a silver electrode with a thickness of 80 nm is evaporated on the substrate containing the fullerene single crystal film and the TMTES-PEN single crystal film in step 1).
  • the voltage conversion curve is a curve showing how the output voltage (V out ) changes with the input voltage (V in ); the definition of voltage gain (gain) can be described by the formula dV out /dV in .
  • V DD ideal power supply voltage
  • gain gain
  • Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the growth temperature is reduced by 10° C., that is, the growth temperature is 25° C., and the rest is the same as Example 1.
  • the specific materials and parameters are shown in Table 1.
  • the low growth temperature causes the volatilization of the solvent at the triple line to be too slow, so that the nucleation density of C60 fullerene is insufficient, and therefore no C60 fullerene crystals are generated.
  • Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the growth temperature is increased by 10° C., that is, the growth temperature is 45° C., and the rest is the same as Example 1.
  • the specific materials and parameters are shown in Table 1.
  • the high growth temperature causes the solvent to evaporate too quickly, which in turn leads to an excessively high nucleation density at the triple line, and the crystal nuclei have sufficient solute for growth, ultimately forming C60 fullerene crystals with disordered orientation and uneven morphology.
  • Comparative Example 3 The difference between Comparative Example 3 and Example 2 is that only carbon tetrachloride is used as the solvent, and the rest is the same as Example 2.
  • the specific materials and parameters are shown in Table 1.

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Abstract

一种富勒烯单晶薄膜及其制备方法和用途，涉及有机半导体技术领域。包括如下步骤：1)富勒烯和溶剂混合，形成混合液；2)采用溶液剪切法使所述混合液中的富勒烯在基底表面结晶生长，获得所述的富勒烯单晶薄膜。通过直接调控三相线处富勒烯的成核密度，并利用三相线的连续移动制备大面积的富勒烯单晶薄膜，其具有取向均一、均匀度高、覆盖率高的优点，此外，具有优异的电子传输性能，能满足光电领域的应用需求。

Description

一种富勒烯单晶薄膜及其制备方法和用途 技术领域
本发明涉及有机半导体技术领域，特别是涉及一种富勒烯单晶薄膜及其制备方法和用途。
背景技术
作为光电领域的明星材料，富勒烯在有机电子学的众多领域如有机太阳能电池、有机场效应晶体管、有机发光二极管、有机光探测器等存在广泛的应用前景。到目前为止，富勒烯的这些应用均已在实验室阶段得到了验证。然而，富勒烯在光电领域仍然没有实现工业化应用。这主要是由于目前富勒烯薄膜的制备方法通常为蒸镀法。蒸镀法需要高温(＞400℃)、高真空的严苛条件且需要昂贵的设备(ACS Nano 2013,7,10,9122-9128)，这些因素导致富勒烯的制备需要高成本和高能耗，不利于其工业化生产应用。此外，蒸镀法得到的富勒烯薄膜相对于富勒烯晶体而言具有较高的缺陷态密度，对其光电性能如电子迁移率、激子扩散距离等造成不利影响。
因此，通过低成本的溶液法制备富勒烯晶体是十分必要的。事实上，相对于其他平面型共轭有机半导体而言，富勒烯由于其独特的零维构型而导致其结晶过程更难以控制。这主要表现为以下两点：一方面，富勒烯分子之间的接触面积相对于平面型分子而言小很多，导致其结晶的驱动力较弱；另一方面，由于富勒烯分子零维的特性导致其易旋转并且无优势的取向。制备富勒烯晶体传统的方法包括液-液界面析出法(Small 2018,14,11,e1703624.)、超分子凝胶结晶法(Adv.Sci.2022,9,2203662)等。其中最常见的方法为液-液界面析出法，其利用富勒烯的良溶剂和不良溶剂界面处溶剂的缓慢混合，使富勒烯在界面处过饱和，从而促进晶体的成核和生长。尽管该方法已经受到广泛的关注和研究，然而其存在一些严重的缺陷，如晶体的成核和生长过程的不可控性导致实验重复性差、富勒烯晶体的尺寸分布混乱等；并且液-液界面析出法为非原位生长过程，需要复杂的转移过程才能对晶体进行光电应用，转移过程不可避免地对晶体造成损害，并导致器件的小型化和集成化是困难的。
综上，为实现富勒烯的实际应用，采用溶液法原位制备富勒烯的单晶薄膜是十分重要的。近年来，已有科学家针对该难题做出了尝试，如Li等人(J.Am.Chem.Soc.2012,134,2760-2765)采用液滴固定结晶法得到了长达数百微米的富勒烯单晶，然而该方法需要在基底中心放置固定物以防止液滴滑动，导致其很难连续制备具有高覆盖率的富勒烯单晶薄膜，类似的方法如聚二甲基硅氧烷(PDMS)辅助生长法(Adv.Mater.2015,27,4371-4376)同样存在该问题。更重要的是，这两种方法制备得到的富勒烯晶体尽管呈现出一定的取向，但其取向分布相对混 乱，同一基底的不同晶体甚至会呈现出完全垂直的取向，因此极大地限制了制得的富勒烯单晶薄膜进行集成化的器件应用。Zheng等人(Carbon.2018,126,299-304)采用浸涂法得到了毫米级的富勒烯晶体薄膜，然而该法得到的富勒烯晶体具有较差的形貌(锯齿状形貌、晶体厚度不均匀等)，且其厚度在亚微米级，不利于载流子注入及垂直器件的构筑。此外，该法需要将基底从本体溶液中拉出，造成原料的大量浪费。Jie等人(Adv.Funct.Mater.2021,31,2105459)采用溶液相外延法制备了英寸级的富勒烯单晶纳米线阵列，但该方法需要光刻胶阵列作为辅助生长层，导致得到的富勒烯单晶阵列在基底上的覆盖率仅约9％，且除去光刻胶阵列的过程中会对富勒烯晶体造成破坏。上述方法除了具有生长不连续、取向混乱、覆盖率低等缺点，其得到的富勒烯晶体的均匀性也较差，具体表现为晶体的高度和宽度差异大，基于富勒烯晶体制备的晶体管其性能具有较大的变异系数，如2021年Jie等人(Adv.Funct.Mater.2021,31,2105459)基于C60富勒烯单晶阵列制备的晶体管其迁移率变异系数高达42.9％，这对于实际应用来说同样是不利的。
除以上问题外，目前基于溶液法制备富勒烯单晶薄膜的另一难点在于调控晶体的形貌。由于富勒烯分子呈现球型或椭球型，导致富勒烯晶体中分子间会有较大的间隙，因此溶剂易进入富勒烯晶体中形成溶剂化晶体。也就是说，溶剂将直接影响富勒烯晶体的构成，对富勒烯晶体的形貌产生重大的影响。如Park等人(Chem.Commun.2009,32,4803-4805)证明溶剂的几何构型会对富勒烯晶体的形貌产生影响，在伪三维溶剂如四氯化碳中可得到六边形晶体，而在间位取代的伪二维苯类溶剂中得到的是一维针状晶体。因此，对于溶液法制备富勒烯单晶薄膜而言，溶剂的选择和调控是至关重要的。为得到覆盖率高并且具有良好取向的富勒烯单晶薄膜，通过溶剂工程将富勒烯晶体的形貌调控成条带状是十分有利的。
综上所述，为实现富勒烯在工业界的实际应用，最理想的富勒烯薄膜是通过溶液法原位制备的、覆盖率高的、取向均一的、均匀度高且可连续制备的大面积单晶薄膜。但是现有技术无法制备上述理想的富勒烯单晶薄膜，该领域主要存在以下三方面的挑战：1)富勒烯晶体生长过程复杂，缺乏对成核和生长过程的整体调控；2)现有原位制备富勒烯晶体薄膜的方法往往需要外部环境如PDMS、光刻胶阵列等辅助晶体的生长，导致制得的富勒烯晶体薄膜存在生长不连续、取向混乱、覆盖率低、均匀性差等缺陷；3)富勒烯晶体的形貌极大地依赖于溶剂的选择，如何通过溶剂工程以尽可能得到兼具良好取向和高覆盖率的富勒烯单晶薄膜仍然是一个谜题。因此，通过溶液法原位制备理想的大面积富勒烯单晶薄膜仍然是一个巨大的技术难题，也是实现富勒烯光电器件的集成化、工业化的前提。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种富勒烯单晶薄膜及其制备方法和用途。
本发明的第一方面保护一种利用气液固三相界面制备富勒烯单晶薄膜的方法，包括如下步骤：
1)富勒烯和溶剂混合，形成混合液；
2)采用溶液剪切法使所述混合液中的富勒烯在基底表面结晶生长，获得所述的富勒烯单晶薄膜。
所述1)中，所述富勒烯选自C60、C70、C76、C78、C80和C84中的一种或多种。
优选的，所述富勒烯选自C60和C70中的一种或两种。
所述1)中，所选溶剂选自邻二甲苯、2-甲基噻吩、2-氯噻吩、2-氯呋喃、3-甲基噻吩、2-乙基噻吩、间二甲苯、间二氟苯、氯苯、邻二氯苯、1,2,4-三氯苯、四氢萘、1-甲基萘、二硫化碳、1,1,2,2-四氯乙烷、四氯化碳、2-甲氧基噻吩、苯乙醚、2-氯-3-甲基噻吩和2,5-二氯噻吩中的一种或多种。
所述1)中，以混合液的总体积为基准计，所述富勒烯的浓度为0.2～20mg/mL。
优选的，为0.4mg/mL～10mg/mL。
所述2)中，所述基底的材质选自硅、氧化铟锡、玻璃、石英、蓝宝石、聚酰亚胺和聚对苯二甲酸乙二酯中的一种或多种。
优选的，所述基底上设有润湿层。
更优选的，所述润湿层的材质选自苯并环丁烯、聚乙烯醇、交联聚甲基丙烯酸甲酯、交联聚苯乙烯、氧化铝、氧化钛、氧化锌、乙氧基化的聚乙烯亚胺、苯基三氯硅烷、金和铝中的一种或多种。
所述2)中，所述溶液剪切法为采用在所述基底上设置剪切工具，使得所述混合液位于所述剪切工具和所述基底之间，并使所述基底或所述剪切工具以一定线速度运行。
优选的，所述剪切工具选自不锈钢光棒、不锈钢线棒、聚四氟乙烯棒、刮刀和涂布头中的一种或多种。
优选的，所述剪切工具和所述基底的间距为20μm～400μm。
更优选的，所述剪切工具和所述基底的间距为50μm～200μm。
优选的，所述溶液剪切法中的线速度为1μm/s～1mm/s。
更优选的，所述溶液剪切法中的线速度为5μm/s～200μm/s。
所述2)中，结晶生长的温度为20℃～120℃。
优选的，所述结晶生长的温度为25℃～60℃。
本发明的第二方面保护如上文所述的制备方法得到的富勒烯单晶薄膜。
本发明的第三方面保护如上文所述的富勒烯单晶薄膜在制备光电器件中的用途。
本发明的第四方面保护一种光电器件，包括如上文所述的富勒烯单晶薄膜。
优选的，所述光电学器件选自有机场效应晶体管、有机太阳能电池、有机互补反相器、有机电路、有机发光二极管、有机记忆存储器、有机光探测器和有机热电器件中的一种或多种。
与现有技术相比，本发明具有如下有益效果：
本发明通过直接调控三相线处富勒烯的成核密度，并利用三相线的连续移动制备大面积的富勒烯单晶薄膜。此外通过调控溶剂来调控富勒烯晶体的形貌，以得到取向均一、均匀度高、覆盖率高的大面积富勒烯单晶薄膜，该大面积富勒烯单晶薄膜具有目前最高的覆盖率(可大于95％)。
采用本发明高质量的富勒烯单晶薄膜，能实现富勒烯在有机电子学中众多领域的实际应用。其中，基于C60富勒烯单晶薄膜的有机场效应晶体管(Organic field-effect transistors,OFETs)阵列的迁移率和阈值电压的变异系数均小于15％，为目前基于C60富勒烯单晶薄膜制备的OFETs中最均匀的性能值；基于C70富勒烯单晶薄膜的有机场效应晶体管可实现0.195cm2V-1s-1的迁移率，为目前基于C70富勒烯单晶制备的OFETs中最高的迁移率。其他应用如有机太阳能电池、有机互补反相器等同样表现出优异的性能。
附图说明
图1显示为本申请实施例1制得的C60富勒烯单晶薄膜整体和局部放大的光学显微镜图。
图2显示为本申请实施例2制得的C60富勒烯单晶薄膜的光学显微镜照片。
图3显示为本申请实施例3制得的C60富勒烯单晶薄膜的光学显微镜照片。
图4显示为本申请实施例4制得的C60富勒烯单晶薄膜的光学显微镜照片。
图5显示为本申请实施例5制得的C60富勒烯单晶薄膜的光学显微镜照片。
图6显示为本申请实施例6制得的C60富勒烯单晶薄膜的光学显微镜照片。
图7显示为本申请实施例7制得的C60富勒烯单晶薄膜的光学显微镜照片。
图8显示为本申请实施例8制得的C70富勒烯单晶薄膜整体和局部放大的光学显微镜图。
图9显示为本申请实施例9制得的C70富勒烯单晶薄膜的光学显微镜照片。
图10显示为本申请实施例10中采用C60富勒烯单晶薄膜制备的场效应晶体管阵列的表征。其中，(a)和(b)分别为70个器件的转移特性曲线及典型的输出特性曲线，其中(a)中的插图为有机场效应晶体管的结构示意图；(c)和(d)分别为70个器件的迁移率及阈值电压统计图。
图11显示为本申请实施例11中采用C70富勒烯单晶薄膜制备的场效应晶体管的典型的转移特性曲线与输出特性曲线。
图12显示为本申请实施例12中基于C60富勒烯单晶薄膜制得的有机太阳能电池的结构示意图及其J-V曲线。其中，(a)为结构示意图，(b)为J-V曲线。
图13显示为本申请实施例13中基于C60富勒烯单晶薄膜制得的有机互补反相器的光学显微镜图及其性能曲线。其中，(a)为光学显微镜图，(b)为电压转换曲线，其中的插图为有机互补反相器的电路示意图，(c)为电压增益曲线。
图14显示为本申请中对比例1制得的薄膜的光学显微镜照片。
图15显示为本申请中对比例2制得的薄膜的光学显微镜照片。
图16显示为本申请中对比例3制得的薄膜的光学显微镜照片。
图17显示为本申请中对比例4制得的薄膜的光学显微镜照片。
具体实施方式
发明人发现采用现有技术制备的富勒烯薄膜存在结晶度低、面积小、取向混乱、覆盖率低、均匀性差等缺点，经大量研究发现，采用溶液剪切法可使富勒烯在基底表面结晶生长，通过溶剂工程与空气-溶液-基底三相线处晶体成核生长行为的调控，成功制备了高质量的大面积富勒烯单晶薄膜，其覆盖率高、取向均一、结晶度高、均匀性好。本发明的富勒烯单晶薄膜满足了富勒烯材料在光电领域的应用需求，可应用于有机场效应晶体管、有机太阳能电池、有机电路等领域中。
本发明采用如下技术方案：
本发明的第一方面保护一种利用气液固三相界面制备富勒烯单晶薄膜的方法，包括如下步骤：
1)富勒烯和溶剂混合，形成混合液；
2)采用溶液剪切法使所述混合液中的富勒烯在基底表面结晶生长，获得所述的富勒烯单晶薄膜。
本申请的方法不需要额外的固定物或光刻胶阵列来辅助结晶，通过调控空气-溶液-基底 三相线处的溶剂挥发促进晶体成核和三相线的连续移动促进取向的富勒烯晶体的连续生长，因此可以得到高覆盖率、可规模化制备的大面积富勒烯单晶薄膜。
本发明所述的方法中，1)中，所述富勒烯选自C60、C70、C76、C78、C80和C84中的一种或多种。优选的，为C60、C70。
本发明所述的方法中，1)中，所选溶剂选自邻二甲苯、2-甲基噻吩、2-氯噻吩、2-氯呋喃、3-甲基噻吩、2-乙基噻吩、间二甲苯、间二氟苯、氯苯、邻二氯苯、1,2,4-三氯苯、四氢萘、1-甲基萘、二硫化碳、1,1,2,2-四氯乙烷、四氯化碳、2-甲氧基噻吩、苯乙醚、2-氯-3-甲基噻吩和2,5-二氯噻吩中的一种或多种。所述溶剂可以为单一一种溶剂，例如2-氯噻吩、2-氯-3-甲基噻吩、2-甲氧基噻吩、3-甲基噻吩、2-乙基噻吩和邻二甲苯。富勒烯晶体极易在晶体内部耦合溶剂分子形成溶剂化晶体，因此富勒烯晶体在不同溶剂中往往呈现出不同的形貌，如C60富勒烯在溶剂间二甲苯中通常会呈现针状晶体，而在溶剂四氯化碳中通常呈现出六边形晶体。为实现富勒烯单晶薄膜在基底上尽可能高的覆盖率，本发明尽可能选择可得到兼具良好取向和高覆盖率带状晶体的溶剂。当晶体在单一溶剂呈现出其他形貌时，可选择加入第二种溶剂调控晶体形貌，如C60富勒烯晶体在四氯化碳中呈现出无取向、不连续且覆盖率低的六边形晶体，可选择加入间二甲苯、3-甲基噻吩、甲苯等可形成针状晶体的溶剂，从而结合两种形貌特征以形成具有良好取向和高覆盖率的条带状晶体，二种溶剂可使得富勒烯单晶薄膜的覆盖率提高至少8倍以上。例如，所述溶剂可以为二种及二种以上溶剂的混合物，例如3-甲基噻吩和四氯化碳、2-氯噻吩和间二甲苯、2-氯噻吩和2-甲基噻吩。再例如，当溶剂为3-甲基噻吩和四氯化碳的混合物时，3-甲基噻吩和四氯化碳的体积比为1:(1～5)，也可以为1:(1～2.5)、1:(2～4.2)、1:(3.6～5)，具体地可以为1:3；当溶剂为2-氯噻吩和间二甲苯的混合物时，2-氯噻吩和间二甲苯的体积比为(1～6):1，也可以为(1～3):1、(1.5～4.6):1、(3.6～5.8):1、(4.2～6):1，具体地可以为4:1；当溶剂为2-氯噻吩和间二甲苯的混合物时，2-氯噻吩和间二甲苯的体积比为(1～15):1，也可以为(1～4.2):1、(3.4～5.6):1、(4.8～10.3):1、(8.6～15):1，具体地可以为9:1。
本发明所述的方法中，1)中，以混合液的总体积为基准计，所述富勒烯的浓度为0.2～20mg/mL，例如可以为0.4mg/mL～2.2mg/mL、2.8mg/mL～3.2mg/mL、2.9mg/mL～4.6mg/mL、3.6mg/mL～6.1mg/mL、5.7mg/mL～7.2mg/mL、6.9mg/mL～9.2mg/mL、8.3mg/mL～10mg/mL、0.4mg/mL～10mg/mL。在某些具体实施方式中为，0.45mg/mL、3mg/mL、6mg/mL、7.5mg/mL、9mg/mL、10mg/mL。
本发明所述的方法中，2)中，所述基底的材质选自硅、氧化铟锡、玻璃、石英、蓝宝石、 聚酰亚胺和聚对苯二甲酸乙二酯中的一种或多种。优选的，为硅、氧化铟锡(ITO)，例如基底为重掺杂磷或硼的硅片。在某个具体实施方式中为表面含一层厚度为285nm二氧化硅的重掺杂磷硅片。
本发明所述的方法中，2)中，所述基底上设有润湿层。优选的，所述润湿层的材质选自苯并环丁烯(BCB)、聚乙烯醇(PVA)、交联聚甲基丙烯酸甲酯(c-PMMA)、交联聚苯乙烯(c-PS)、氧化铝(Al2O3)、氧化钛(TiO2)、氧化锌(ZnO)、乙氧基化的聚乙烯亚胺(PEIE)、苯基三氯硅烷(PTS)、金(Au)、铝(Al)等。所述润湿层的制备方法可为旋涂法(聚合物)、蒸镀法(金属)、溶胶-凝胶法(金属氧化物)、气相法(自组装单层)，如当材质为聚合物时，如PVA、c-PMMA、c-PS，采用旋涂法；当材质为金属时，如Au、Al，采用蒸镀法；当材质为金属氧化物时，如Al2O3、TiO2、ZnO，采用溶胶-凝胶法；当材质为自组装单层时，如PTS，采用气相法。在某些具体实施方式中，所述润湿层的材质为BCB、c-PMMA、Au、PEIE、PTS。
本发明所述的方法中，2)中，所述溶液剪切法为采用在所述基底上设置剪切工具，使得所述混合液位于所述剪切工具和所述基底之间，并使所述基底或所述剪切工具以一定线速度运行，优选所述基底以一定线速度运行，运行结束后在所述基底上获得了具有高覆盖率的大面积富勒烯单晶薄膜。优选的，所述剪切工具选自不锈钢光棒、不锈钢线棒、聚四氟乙烯棒、刮刀和涂布头中的一种或多种。在某个具体实施方式中，为不锈钢光棒。优选的，所述剪切工具和所述基底的间距为20μm～400μm，例如为50μm～150μm、100μm～250μm、200μm～350μm、300μm～400μm、50μm～200μm、100μm。优选的，所述溶液剪切法中的线速度为1μm/s～1mm/s，例如为5μm/s～105μm/s、58μm/s～155μm/s、126μm/s～205μm/s、189μm/s～450μm/s、350μm/s～600μm/s、550μm/s～780μm/s、700μm/s～950μm/s、820μm/s～1mm/s、8μm/s、10μm/s、12μm/s、15μm/s、20μm/s。
本发明所述的方法中，2)中，所述结晶生长的温度为20℃～120℃，例如可以为20℃～45℃、36℃～58℃、47℃～78℃、62℃～96℃、84℃～105℃、96℃～120℃、25℃～60℃。在某些具体实施方式中为，25℃、30℃、35℃、40℃、45℃、50℃、60℃。由于富勒烯晶体生长的困难性，需要对基底温度、剪切速度、溶液浓度等生长条件进行精细调控以调控晶体的成核和生长过程。例如，当温度过高时，由于溶剂挥发过快，气液固三相线处的成核密度过高，且晶核的各个方向都有足够的溶质可以生长，导致富勒烯晶体的取向混乱且形貌变差如粗糙度等增加，此时可提高线速度、降低混合液的浓度；而当温度过低时，由于溶剂挥发过慢而导致三相线处成核困难，只能形成一些无序的非晶，此时可降低线速度、提高混合液的浓度。
本发明第二方面保护如上文所述的制备方法得到的富勒烯单晶薄膜。本发明的富勒烯单晶薄膜在基底上的覆盖率可高达90％以上。所述覆盖率是采用光学显微镜观察富勒烯单晶薄膜后，通过ImageJ软件分析获得。
本发明第三方面保护如上文所述富勒烯单晶薄膜在制备光电器件中的用途。
本发明第四方面保护一种光电器件，包括如上文所述的富勒烯单晶薄膜。
本发明所述光电器件中，所述光电器件选自有机场效应晶体管、有机太阳能电池、有机互补反相器、有机电路、有机发光二极管、有机记忆存储器、有机光探测器和有机热电器件中的一种或多种。
当所述光电器件为有机场效应晶体管时，所述有机场效应晶体管的制备方法如下:
1)在如上文所述富勒烯单晶薄膜上制备源漏电极，获得所述的有机场效应晶体管。
所述源漏电极为源极(Source，S)和漏极(Drain，D)的总称，源极和漏极之间的电压、电流分别由VDS、IDS表示。当栅电极(Gate，G)上施加电压时，电场通过栅绝缘层(Gate Dielectric)影响源极和漏极之间的电流。
优选的，所述源漏电极的制备方法选自蒸镀法、转移法和打印法中的一种或多种。
优选的，所述源漏电极选自银、氟化锂/铝、金、石墨烯、钙和镁中的一种或多种。
当所述光电器件为有机太阳能电池时，所述有机太阳能电池的制备方法如下:
1)在如上文所述的富勒烯单晶薄膜上制备给体材料层，得到双层结构膜；
2)在所述双层结构膜上制备顶电极，获得所述的有机太阳能电池。
优选的，所述给体材料层的材质选自给体小分子和给体聚合物。更优选的，所述给体小分子选自2-((7-(4-(二甲苯基氨基)苯基)苯并[C][1,2,5]噻二唑-4-基)亚甲基)丙二腈(DTDCPB)，所述给体聚合物选自聚(3-己基噻吩-2,5-二基)(P3HT)。
优选的，1)中，所述给体材料层的制备方法选自旋涂法和蒸镀法中的一种或两种。
优选的，2)中，所述顶电极选自金、三氧化钼/银、铂、钛、铬等。
优选的，2)中，所述顶电极的制备方法选自蒸镀法、转移法和打印法中的一种或多种。
当所述光电器件为有机互补反相器时，所述有机互补反相器的制备方法如下:
1)在如上文所述的富勒烯单晶薄膜的基底的另一侧生长p型半导体薄膜。
2)在含富勒烯单晶薄膜和p型半导体薄膜的基底上蒸镀电极，获得所述的有机互补反相器。
所选优选的，1)中，所述p型半导体薄膜的生长方法选自溶液剪切法、液滴固定结晶法、蒸镀法和物理气相传输法中的一种或多种。
优选的，1)中，所述p型半导体薄膜的材质选自并杂环及苯并杂环类衍生物、并苯类化合物及其衍生物、寡聚噻吩类衍生物和卟啉类衍生物中的一种或多种。
优选的，2)中，所述电极选自银和金中的一种或多种。
采用本发明方法得到的富勒烯单晶薄膜的覆盖率大于95％，具有面积大、均匀度高、取向均一的优点。采用本发明的C60富勒烯单晶薄膜得到的有机场效应晶体管阵列，具有良好的电子传输性能，有机场效应晶体管阵列的最高电子迁移率超过1cm2V-1s-1，电子迁移率的变异系数仅为13.3％，远低于现有文献中报道的42.9％；采用C70单晶薄膜得到的有机场效应晶体管阵列可实现0.195cm2V-1s-1的电子迁移率，远高于现有文献中报道的0.0132cm2V-1s-1。采用本发明的C60富勒烯单晶薄膜得到的有机太阳能电池展现出良好的光伏效应，光电转化效率可达0.123％。采用本发明所述的富勒烯单晶薄膜得到的有机互补反相器，几乎没有电压损失，电压增益高。综合说明，本发明方法得到的富勒烯单晶薄膜在光电领域、互补电路集成领域具有实际的应用潜力。
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
在进一步描述本发明具体实施方式之前，应理解，本发明的保护范围不局限于下述特定的具体实施方案；还应当理解，本发明实施例中使用的术语是为了描述特定的具体实施方案，而不是为了限制本发明的保护范围；在本发明说明书和权利要求书中，除非文中另外明确指出，单数形式“一个”、“一”和“这个”包括复数形式。
当实施例给出数值范围时，应理解，除非本发明另有说明，每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义，本发明中使用的所有技术和科学术语与本技术领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外，根据本技术领域的技术人员对现有技术的掌握及本发明的记载，还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。
实施例1-9
本实施例1-9，参照表1中的物料和参数制备大面积富勒烯单晶薄膜，制备方法包括如下步骤：
1)以硅片或石英片或ITO为基底，在基底上修饰润湿层，然后将含润湿层的基底置于加热台上加热。当润湿层的材质为聚合物如BCB、c-PMMA、PEIE时，采用旋涂法；当润湿 层的材质为Au时，采用蒸镀法；当润湿层的材质为PTS时，采用气相法。其中，硅片为表面含一层厚度为285nm二氧化硅的P型高掺杂硅片。
2)将富勒烯和溶剂混合形成混合液，通过超声使混合液充分混合均匀，将混合液通过距离基底的上表面约100μm处的不锈钢光棒注入不锈钢光棒与基底的空隙中。待混合液稳定后使加热台以恒定线速度运动。运行结束后即在基底上获得了大面积富勒烯单晶薄膜。
采用光学显微镜对上述实施例1-9得到的富勒烯单晶薄膜进行形貌表征，结果见图1-9。
从图1中a可知，采用本申请的方法可获得大面积的富勒烯单晶薄膜；从图1中b可知，实施例1获得的C60富勒烯单晶薄膜中，每根晶体之间具有相同的取向和相近的颜色，且晶体无明显的形貌缺陷如裂纹、空洞、树枝状形貌等，表明本申请的方法可获得取向均一、高度均匀的高质量富勒烯单晶薄膜。更进一步的，通过ImageJ软件分析单晶薄膜的覆盖率，从图1中b可知，晶体覆盖率高达84％。
从图2-9可知，采用本申请的方法获得的C60富勒烯、C70富勒烯单晶薄膜的每根晶体之间均具有相近的取向与颜色，且最高的覆盖率可大于95％，即获得了取向均一、高度均匀、覆盖率高的富勒烯单晶薄膜。
实施例1-9中富勒烯单晶薄膜的覆盖率的具体数值见表1。
表1

实施例10
本实施例10中，采用实施例1得到的C60富勒烯单晶薄膜制备有机场效应晶体管阵列，包括如下步骤：
在实施例1制得的C60富勒烯单晶薄膜上蒸镀源漏电极，也即将掩膜版固定在C60富勒烯单晶薄膜上，依次蒸镀1nm LiF和80nm Al作为源漏电极，同时分别以基底的高掺杂硅、二氧化硅/BCB作为栅极电极和栅极绝缘层，得到有机场效应晶体管阵列。
本实施例中得到70个有机场效应晶体管。
在手套箱内采用半导体参数分析仪测定70个有机场效应晶体管的N型转移特性曲线(栅极电压VG:-10～40V；源漏电压VDS:40V)及输出特性曲线(栅极电压VG:0～40V,step为8V；源漏电压VDS:0～40V)。从转移特性曲线中提取电子迁移率(mobility,μ)和阈值电压(threshold voltage,VT)并计算平均值和变异系数σ(变异系数＝标准偏差/平均值×100％)。结果见图10。
对于有机场效应晶体管，其性能主要取决于迁移率、阈值电压等性能参数，其中，迁移率是对有机场效应晶体管的性能起决定性作用的参数，迁移率是载流子在单位电场强度下的迁移速率，通常迁移率越高，有机场效应晶体管的性能越好；阈值电压是使晶体管开启所必需的最低栅极电压，阈值电压的绝对值越低越好。
从图10可知，70个有机场效应晶体管均实现了良好的运行且其转移特性曲线(图10a)具有良好的重合度。本发明的C60单晶薄膜具有良好的电子传输性能，其最高电子迁移率超过1cm2V-1s-1，满足了大部分有机电路、传感应用或柔性显示的需求；电子迁移率和阈值电压的变异系数分别为13.3％(图10c)和11.4％(图10d)，表明本发明制得的富勒烯单晶薄膜具有相当好的均匀性。该变异系数值远低于2021年Jie等人基于C60单晶阵列制备的晶体管，其电子迁移率的变异系数高达42.9％(Adv.Funct.Mater.2021,31,2105459)。
实施例11
本实施例11，以实施例8的C70富勒烯单晶薄膜为基础制备有机场效应晶体管。包括如下：
其基本流程同10，不同点在于蒸镀的源漏电极为Ag，其余均同。
在手套箱内采用半导体参数分析仪测定有机场效应晶体管的N型转移特性曲线(VG:-10～50V；VDS:50V)与输出特性曲线(VG:0～50V,step为10V；VDS:0～50V)，结果见图11。
开关比(Ion/Ioff)是有机场效应晶体管的一个重要性能指标，表示有机场效应晶体管在导通状态和截止状态下的电流比值，开关比越大，有机场效应晶体管的性能越好。
从图11可知，基于C70富勒烯单晶薄膜制备的有机场效应晶体管的电子迁移率高达0.195cm2V-1s-1，为目前基于C70富勒烯单晶的OFETs的最高值。现有技术中C70富勒烯单晶的电子迁移率最高仅0.0132cm2V-1s-1(Chemical Physics Letters.2022,807,140094)，
实施例12
本实施例12中，以实施例7的C60富勒烯单晶薄膜为基础制备有机太阳能电池。包括如下：
1)在实施例7的C60富勒烯单晶薄膜上采用蒸镀法制备一层厚度为60nm的DTDCPB形成双层结构膜。
2)在双层结构膜上蒸镀厚度为10nm的三氧化钼和80nm的银作为顶电极，获得有机太阳能电池。
3)在手套箱内用太阳光模拟器照射步骤2)得到的有机太阳能电池，并用半导体参数分析仪获得电流密度-电压(Current density，J-V)曲线，基于J-V曲线获得开路电压(Voc)、短路电路(Jsc)、填充因子(FF)和光电转换效率(PCE)，结果见图12。
开路电压(Voc)是指在没有电流回路(正负电极断路)时经过光照后器件产生的电压，即太阳能电池的最大输出电压，单位为V；短路电流(Jsc)是指在外加电场为零时，受光照的器件在形成回路(正负电极短路)时所能产生的电流，即太阳能电池的最大输出电流；单位为A/cm2或mA/cm2。填充因子(FF)是电池具有最大输出功率时的电流和电压的乘积与短路电流和开路电压乘积的比值。能量转换效率(PCE)是指太阳能电池将太阳能转化为电能的效率。
从图12可知，基于本申请的高覆盖率富勒烯单晶薄膜制得的有机太阳能电池表现出良好的光伏效应，光电转化效率可达0.123％，表明富勒烯单晶薄膜在光电领域具有实际的应用潜力。
实施例13
本实施例13中，以实施例1的C60富勒烯单晶薄膜为基础制备有机互补反相器。
1)在实施例1的含C60富勒烯单晶薄膜的基底的另一侧生长1,4,8,11-四甲基-6,13-(三乙基甲硅烷基乙炔基)并五苯(TMTES-PEN)的单晶薄膜。生长方法为与制备实施例1的富 勒烯单晶薄膜相同的溶液剪切法，不同点在于溶剂和TMTES-PEN形成的混合液的浓度、基底温度和剪切速度分别为间二甲苯、8mg/mL、40℃、50μm/s。
2)在步骤1)的含富勒烯单晶薄膜和TMTES-PEN单晶薄膜的基底上蒸镀厚度为80nm的银电极。
3)在手套箱中用半导体分析仪测试有机互补反相器的电压转换曲线以及电压增益曲线。
电压转换曲线是输出电压(Vout)随输入电压(Vin)的变化而变化的曲线；电压增益(gain)的定义可以由公式dVout/dVin描述。
从图13可知，电压转换曲线(图13b)中发生电压翻转的位置接近理想的电源电压(VDD)的1/2处(约为20V)，几乎没有电压损失，且当有机互补反相器VDD＝40V时的电压增益(gain)可达63.5(图13c)。良好的电压翻转特性表明本申请的富勒烯单晶薄膜具有应用于互补集成电路的潜力。
对比例1
本对比例1与实施例1不同点在于，生长温度降低了10℃，也即生长温度为25℃，其余均同实施例1，具体物料和参数见表1。
采用光学显微镜对对比例1得到的薄膜进行形貌表征，结果见图14。
从图14可知，生长温度低导致三相线处溶剂的挥发过慢，从而C60富勒烯的成核密度不足，因此没有C60富勒烯晶体的生成。
对比例2
本对比例2与实施例1不同点在于，生长温度升高了10℃，也即生长温度为45℃，其余均同实施例1，具体物料和参数见表1。
采用光学显微镜对对比例2得到的薄膜进行形貌表征，结果见图15。
从图15可知，生长温度高导致溶剂挥发过快，进而导致三相线处成核密度过高，且晶核有充足的溶质可供生长，最终形成取向混乱、形貌不均匀的C60富勒烯晶体。
对比例3
本对比例3与实施例2不同点在于，仅仅采用四氯化碳作为溶剂，其余均同实施例2，具体物料和参数见表1。
采用光学显微镜对对比例3得到的薄膜进行形貌表征，结果见图16。
从图16可知，仅使用四氯化碳作为溶剂时，仅能得到一些面积小且不连续的多边形晶体，这与文献报道的一致(Chem.Commun.2009,4803-4805)。而当使用四氯化碳和3-甲基噻吩的混合溶剂时，可结合六边形晶体和一维晶体的特性，得到兼具高覆盖率和良好取向的条带状 晶体(图2)，覆盖率提高8倍以上。该结果表明在富勒烯晶体制备过程中通过溶剂选择可极大地改善富勒烯晶体的形貌，促进其在诸多领域的实际应用。
对比例4
本对比例4与实施例3的不同点在于仅仅采用间二甲苯作为溶剂，其余均同实施例3，具体物料和参数见表1。
采用光学显微镜对对比例4得到的薄膜进行形貌表征，结果见图17。
从图17可知，仅使用间二甲苯作为溶剂时，仅能得到覆盖率低、取向混乱且相互堆叠的一维针状晶体。而当使用间二甲苯与2-氯噻吩的混合溶剂时，可得到覆盖率高、取向均一的条带状晶体(图3)，覆盖率提高约5.3倍。该结果表明了在制备富勒烯晶体薄膜过程中溶剂调控的重要性。
以上的实施例是为了说明本发明公开的实施方案，并不能理解为对本发明的限制。此外，本文所列出的各种修改以及发明中方法、组合物的变化，在不脱离本发明的范围和精神的前提下对本领域内的技术人员来说是显而易见的。虽然已结合本发明的多种具体优选实施例对本发明进行了具体的描述，但应当理解，本发明不应仅限于这些具体实施例。事实上，各种如上所述的对本领域内的技术人员来说显而易见的修改来获取发明都应包括在本发明的范围内。

Claims (10)

  1. 一种利用气液固三相界面制备富勒烯单晶薄膜的方法，其特征在于，包括如下步骤：
    1)富勒烯和溶剂混合，形成混合液；
    2)采用溶液剪切法使所述混合液中的富勒烯在基底表面结晶生长，获得所述的富勒烯单晶薄膜。
  2. 如权利要求1所述的方法，其特征在于，包括如下技术特征中的至少一项：
    A1)所述富勒烯选自C60、C70、C76、C78、C80和C84中的一种或多种；
    A2)所选溶剂选自邻二甲苯、2-甲基噻吩、2-氯噻吩、2-氯呋喃、3-甲基噻吩、2-乙基噻吩、间二甲苯、间二氟苯、氯苯、邻二氯苯、1,2,4-三氯苯、四氢萘、1-甲基萘、二硫化碳、1,1,2,2-四氯乙烷、四氯化碳、2-甲氧基噻吩、苯乙醚、2-氯-3-甲基噻吩和2,5-二氯噻吩中的一种或多种；
    A3)以混合液的总体积为基准计，所述富勒烯的浓度为0.2mg/mL～20mg/mL，优选为0.4mg/mL～10mg/mL；
    A4)所述基底的材质选自硅、氧化铟锡、玻璃、石英、蓝宝石、聚酰亚胺和聚对苯二甲酸乙二酯中的一种或多种；
    A5)所述结晶生长的温度为20℃～120℃，优选为25℃～60℃。
  3. 如权利要求2所述的方法，其特征在于，所述基底上设有润湿层。
  4. 如权利要求3所述的方法，其特征在于，所述润湿层的材质选自苯并环丁烯、聚乙烯醇、交联聚甲基丙烯酸甲酯、交联聚苯乙烯、氧化铝、氧化钛、氧化锌、乙氧基化的聚乙烯亚胺、苯基三氯硅烷、金和铝中的一种或多种。
  5. 如权利要求1所述的方法，其特征在于，2)中，所述溶液剪切法为采用在所述基底上设置剪切工具，使得所述混合液位于所述剪切工具和所述基底之间，并使所述基底或所述剪切工具以一定线速度运行。
  6. 如权利要求5所述的制备方法，其特征在于，所述剪切工具选自不锈钢光棒、不锈钢线棒、聚四氟乙烯棒、刮刀和涂布头中的一种或多种；
    和/或，所述剪切工具和所述基底的间距为20μm～400μm，优选为50μm～200μm；
    和/或，所述溶液剪切法中的线速度为1μm/s～1mm/s，优选为5μm/s～200μm/s。
  7. 如权利要求1-6任一项所述的制备方法得到的富勒烯单晶薄膜。
  8. 如权利要求7所述的富勒烯单晶薄膜在光电器件中的用途。
  9. 一种光电器件，其特征在于，包括如权利要求7所述的富勒烯单晶薄膜。
  10. 如权利要求9的光电器件，其特征在于，所述光电器件选自有机场效应晶体管、有机太阳 能电池、有机互补反相器、有机电路、有机发光二极管、有机记忆存储器、有机光探测器和有机热电器件中的一种或多种。
PCT/CN2023/109278 2023-07-05 2023-07-26 一种富勒烯单晶薄膜及其制备方法和用途 Ceased WO2025007376A1 (zh)

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