CN108728794B - Organic self-supporting film, preparation method and application thereof - Google Patents

Organic self-supporting film, preparation method and application thereof Download PDF

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CN108728794B
CN108728794B CN201710271647.1A CN201710271647A CN108728794B CN 108728794 B CN108728794 B CN 108728794B CN 201710271647 A CN201710271647 A CN 201710271647A CN 108728794 B CN108728794 B CN 108728794B
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organic
supporting film
self
free standing
film
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CN108728794A (en
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潘革波
肖燕
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
University of Chinese Academy of Sciences
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
University of Chinese Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0005—Separation of the coating from the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/001—Coating on a liquid substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • 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

Abstract

The invention discloses an organic self-supporting film, a preparation method and application thereof. The organic self-supporting membrane comprises a two-dimensional fishing net structure, the fishing net structure comprises a net rack and a plurality of fishing net mesh-shaped hole structures formed in the net rack, the net rack is formed by interweaving any one or combination of more than two of a plurality of one-dimensional nanowires, nanobelts and nanotubes, and the nanowires, the nanobelts and the nanotubes are all formed by organic nanocrystals. The preparation method comprises the following steps: continuously depositing an organic compound on the surface of a liquid phase system by adopting a physical vapor deposition method to form a continuous organic self-supporting film; the density of the liquid phase system is greater than that of the organic compound, and the organic compound is insoluble in the liquid phase system. The invention does not need any modification and recombination on organic micromolecules, the obtained organic self-supporting film has good crystallinity, transferability and excellent compatibility, the self-supporting film is of a two-dimensional network structure, and all organic nanocrystals can be in direct contact with a target substrate.

Description

Organic self-supporting film, preparation method and application thereof
Technical Field
The invention relates to a self-supporting film, in particular to an organic self-supporting film, a preparation method and application thereof, and belongs to the technical field of organic semiconductor films.
Background
High-quality organic semiconductor films have become a research hotspot due to their potential use in organic light emitting diodes, organic field effect transistors, organic optoelectronic devices, solar cells, organic sensing devices, and the like. At present, various methods such as electrospinning, solution self-assembly, template method, etc. have been developed to prepare such organic semiconductor thin films having high crystallinity. However, the organic thin film prepared by these methods is usually formed by stacking a plurality of organic nanocrystals, and is three-dimensional in the micro-scale range, and such thin film has a problem that the organic nanocrystals on the upper layer of a product cannot be directly contacted with a target substrate, which greatly affects the final performance of the device. In addition, these methods have relatively high requirements on the solubility of small organic molecules, and particularly have great limitations on many organic semiconductor small molecule materials with poor solubility and high mobility. Therefore, the selection and development of a method with a wide application range for preparing the organic semiconductor film with the planar structure in the micro-scale range has very important significance for better exerting the potential application of the organic semiconductor film.
Physical Vapor Deposition (PVD) has been a research focus in recent years due to its advantages of wide application range, simple operation, low cost, controllable final product, etc. However, the conventional PVD methods all use a solid phase as a substrate, and the product and the substrate have strong forces and are difficult to separate, which greatly affects the subsequent device preparation and the final device performance, and a lot of costs are needed to solve the product transfer problem, thereby greatly limiting the potential application of the organic thin film.
Disclosure of Invention
The main objective of the present invention is to provide an organic self-supporting film, a method for preparing the same, and an application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an organic self-supporting film which comprises a two-dimensional fishing net structure, wherein the fishing net structure comprises a net rack and a plurality of fishing net mesh-shaped hole structures formed in the net rack, the net rack is formed by interweaving any one or more than two of a plurality of one-dimensional nanowires, nanobelts and nanotubes, and the nanowires, the nanobelts and the nanotubes are all formed by organic nanocrystals.
In a preferred embodiment, the cross-sectional dimension of the nanowire is 5 to 100nm, and the length is 1 to 1000 μm.
Preferably, the width of the nanobelt is 50-1000 nm, and the length of the nanobelt is 500 nm-100 μm.
Preferably, the inner diameter of the nanotube is 5-50 nm, the outer diameter is 10-100 nm, and the length is 1-1000 μm.
Preferably, the thickness of the organic self-supporting film is 100nm to 100 μm.
Preferably, the organic self-supporting film comprises a planar two-dimensional fishing net structure.
In a preferred embodiment, the fishing net structure includes a plurality of periodic and interconnected fishing net units.
Preferably, 1 to 100 fishing net units are provided in a fishing net structure of 1 to 100 μm.
Preferably, the fishing net structure comprises a regular structure and/or an irregular structure.
Furthermore, the net frame in the regular structure is formed by the combination of one or more than two of a plurality of one-dimensional nanowires, nanobelts and nanotubes which are vertically and horizontally arranged.
Further, in the irregular structure, any one or a combination of two or more of the one-dimensional nanowires, the nanobelts and the nanotubes mutually form a set angle arrangement.
In a preferred embodiment, the net frames of the fishing net structure are all on the same plane.
Preferably, the size of the pore structure is 5 nm-50 μm.
In a preferred embodiment, the organic nanocrystal is composed of an organic compound.
Preferably, the organic compound includes any one or a combination of two or more of an organic semiconductor compound having a planar molecular structure, fullerene, and a derivative thereof.
Preferably, the organic compound includes a fused aromatic organic semiconductor compound.
Further, the fused ring aromatic organic semiconductor compound includes any one or a combination of two or more of acene compounds, metal phthalocyanine compounds, perylene imide derivatives, perylene anhydride compounds, tetrafluoro-p-benzoquinone dimethane metal compounds, metalloporphyrin compounds, rubrene and N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine.
In a preferred embodiment, the organic self-supporting film is further combined with a solid substrate or a liquid substrate.
Further, the solid substrate includes any one of a silicon wafer, glass, PET, paper, aluminum foil, quartz plate, mica, fiber, copper plate, gold plate, and silver plate.
Further, the liquid substrate includes all liquids immiscible with the organic compound.
Further, the liquid base includes any one or a combination of two or more of an organic solvent, water, and an ionic liquid.
The embodiment of the invention also provides a preparation method of the organic self-supporting film, which comprises the following steps: continuously depositing an organic compound on the surface of a liquid phase system by adopting a physical vapor deposition method to form a continuous organic self-supporting film; the density of the liquid phase system is greater than the density of the organic compound, and the organic compound is insoluble in the liquid phase system.
In a preferred embodiment, the preparation method comprises: heating the organic compound to sublimation, and continuously depositing the organic compound on the surface of the liquid-phase system by using the carrier gas, thereby forming the organic self-supporting film. Further, the carrier gas includes nitrogen.
Preferably, the deposition time is 10-320 min, the deposition temperature is 325-625 ℃, and the air flow speed of the carrier is 100-300 ppm.
The degree of crosslinking (i.e., crosslink density) of the organic self-supporting film can be adjusted by varying the deposition time and deposition temperature.
In a preferred embodiment, the liquid phase system comprises an ionic liquid.
Further, the ionic liquid includes a cation and an anion.
Further, the cation includes any one or a combination of two or more of imidazolium salt ion, pyridinium salt ion, piperidinium salt ion, pyrrolium salt ion, morpholinium salt ion and quaternary phosphonium salt ion.
Further, the anion includes any one or a combination of two or more of halogen ion, nitrate, tetrafluoroborate, trifluoromethanesulfonate, acetate, p-toluenesulfonate, diethyl ester and methyl ester ion.
In a preferred embodiment, the organic compound includes any one or a combination of two or more of an organic semiconductor compound having a planar molecular structure, fullerene, and a derivative thereof.
Preferably, the organic compound includes a fused aromatic organic semiconductor compound.
Further, the fused ring aromatic organic semiconductor compound includes any one or a combination of two or more of acene compounds, metal phthalocyanine compounds, perylene imide derivatives, perylene anhydride compounds, tetrafluoro-p-benzoquinone dimethane metal compounds, metalloporphyrin compounds, rubrene and N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine.
In a preferred embodiment, the preparation method further comprises: and stripping the organic self-supporting film on the surface of the liquid phase system.
Further, the preparation method further comprises the following steps: and collecting the organic self-supporting film obtained by surface stripping of the liquid-phase system by using a collecting device.
The embodiment of the invention also provides the application of the organic self-supporting film in the preparation of organic semiconductor devices.
Compared with the prior art, the invention has the advantages that:
1) the organic self-supporting film provided by the invention has good crystallinity, transferability and excellent compatibility, and the organic self-supporting film is of a two-dimensional network structure, all organic nanocrystals can be directly contacted with a target substrate, so that the defect that the application of the traditional organic film is influenced because the traditional organic film is difficult to separate and is not well contacted with the target substrate can be overcome;
2) the preparation method of the organic self-supporting film provided by the invention adopts a physical vapor deposition technology taking liquid as a substrate, is suitable for any organic small molecule, does not need to modify and recombine the organic small molecule, and uses the ionic liquid which is a green solvent and has the recycling property. Therefore, the method has the advantages of wide application range, simplicity in operation, environmental friendliness, energy conservation and the like, and has a very important promoting effect on really realizing the preparation of large-area organic semiconductor devices.
Drawings
FIG. 1 is a schematic diagram of a method for fabricating an organic self-supporting film according to an exemplary embodiment of the present invention;
FIG. 2 is an electron photograph of an organic self-supporting film obtained in example 1 of the present invention;
FIG. 3a is an electron photograph of the organic self-supporting film transferred to the surface of deionized water according to example 1 of the present invention;
FIG. 3b shows the transfer of the organic self-supporting film obtained in example 1 of the present invention to Si/SiO2An electrophotographic image of the surface;
FIG. 4 is an optical microscope photograph of an organic self-supporting film obtained in example 1 of the present invention;
FIG. 5 is a single crystal X-ray diffraction chart of the organic self-supporting film obtained in example 1 of the present invention;
FIG. 6 is an electron photograph showing the appearance of the organic self-supporting film obtained in example 2 of the present invention;
FIG. 7 is an optical microscope photograph of an organic self-supporting film obtained in example 2 of the present invention;
FIG. 8 is an optical microscope photograph of an organic self-supporting film obtained in example 4 of the present invention;
FIG. 9 is an optical microscope photograph of an organic self-supporting film obtained in example 5 of the present invention;
FIG. 10 is an optical microscope photograph of an organic self-supporting film obtained in example 6 of the present invention;
FIG. 11 is an optical microscope photograph of an organic self-supporting film obtained in example 8 of the present invention.
Detailed Description
Aiming at the condition of organic thin films in the prior art, the inventor of the invention provides a technical scheme of the invention through long-term research and a large amount of practice, and provides an organic self-supporting film and a preparation method thereof. The technical solution, its implementation and principles, etc. will be further explained as follows.
An aspect of an embodiment of the present invention provides an organic self-supporting film, which includes a two-dimensional fishing net structure, where the fishing net structure includes a net frame and a plurality of fishing net mesh-like hole structures formed in the net frame, the net frame is formed by interweaving any one or a combination of two or more of a plurality of one-dimensional nanowires, nanobelts, and nanotubes, and the nanowires, nanobelts, and nanotubes are all formed by organic nanocrystals.
In a preferred embodiment, the cross-sectional dimension of the nanowire is 5 to 100nm, and the length is 1 to 1000 μm.
Preferably, the width of the nanobelt is 50-1000 nm, and the length of the nanobelt is 500 nm-100 μm.
Preferably, the inner diameter of the nanotube is 5-50 nm, the outer diameter is 10-100 nm, and the length is 1-1000 μm.
Preferably, the crosslinking density (i.e., the degree of crosslinking) of the organic self-supporting film can be adjusted by varying the deposition time and the deposition temperature.
Preferably, the thickness of the organic self-supporting film is 100nm to 100 μm. The thickness of the organic self-supporting film can be regulated and controlled by adjusting the quality of a deposition source and the deposition time.
Preferably, the organic self-supporting film comprises a planar two-dimensional fishing net structure.
Wherein, the size and the shape of the organic self-supporting film can be regulated and controlled by regulating the size and the shape of the collecting device.
In a preferred embodiment, the fishing net structure includes a plurality of periodic and interconnected fishing net units.
Preferably, 1 to 100 fishing net units are provided in a fishing net structure of 1 to 100 μm.
Preferably, the fishing net structure comprises a regular structure and/or an irregular structure.
Furthermore, the net frame in the regular structure is formed by the combination of one or more than two of a plurality of one-dimensional nanowires, nanobelts and nanotubes which are vertically and horizontally arranged.
Further, in the irregular structure, any one or a combination of two or more of the one-dimensional nanowires, the nanobelts and the nanotubes mutually form a set angle arrangement.
Preferably, the net racks of the fishing net structure are all on the same plane.
Preferably, the size of the pore structure (i.e. the density of the network) is 5nm to 50 μm. The pore structure has good controllability, and can be regulated and controlled by controlling deposition time, airflow speed, deposition temperature and the like.
In a preferred embodiment, the organic nanocrystal is composed of an organic compound.
Preferably, the organic compound is at least one selected from the group consisting of an organic semiconductor compound having a planar molecular structure, a fullerene, and a derivative thereof, or a combination of two or more thereof, but is not limited thereto.
Preferably, the organic compound includes a fused aromatic organic semiconductor compound.
Further, the fused ring aromatic organic semiconductor compound includes any one or a combination of two or more of acene compounds, metal phthalocyanine compounds, perylenes, perylene imide derivatives, perylene anhydride compounds, tetrafluoro-p-benzoquinone dimethane metal compounds, metalloporphyrin compounds, rubrene, and N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, but is not limited thereto.
For example, specifically, the fused aromatic organic semiconductor compound may be copper octaethylporphyrin, platinum octaethylporphyrin, zinc octaethylporphyrin, nickel phthalocyanine, cobalt phthalocyanine, fullerene (C60), pentacene, or the like.
In a preferred embodiment, the organic self-supporting film can be transferred to the surface of various solid substrates or liquid substrates and firmly bonded to the solid substrates or liquid substrates.
Further, the solid substrate includes all solid surfaces of silicon wafer, glass, PET (polyethylene terephthalate), paper, aluminum foil, quartz plate, mica, fiber, copper plate, gold plate, silver plate, etc., but is not limited thereto.
Further, the liquid substrate includes all liquids immiscible with the organic compound.
Further, the liquid base includes any one or a combination of two or more of an organic solvent, water (preferably deionized water), and an ionic liquid, but is not limited thereto.
In a preferred embodiment, the organic self-supporting film is firmly attached to the surface of various solid substrates or liquid substrates and does not fall off under the action of various external forces.
Further, the various external forces include, but are not limited to, solution soaking, bending, solution rinsing, and the like. Wherein, the solution selected for soaking and washing can be ethanol, acetone, water and the like.
Another aspect of an embodiment of the present invention provides a method for preparing an organic self-supporting film, including: continuously depositing organic compounds on the surface of a liquid phase system by adopting a Physical Vapor Deposition (PVD) method to form a continuous organic self-supporting film; the density of the liquid phase system is greater than the density of the organic compound, and the organic compound is insoluble in the liquid phase system.
Further, the preparation method is a physical vapor deposition method.
In a preferred embodiment, the preparation method comprises: heating the organic compound to sublimation, and continuously depositing the organic compound on the surface of the liquid-phase system by using the carrier gas, thereby forming the organic self-supporting film. Further, the carrier gas includes nitrogen.
Preferably, the deposition time is 10-320 min, the deposition temperature is 325-625 ℃, and the air flow speed of the carrier is 100-300 ppm.
In a preferred embodiment, the liquid phase system is selected from ionic liquids.
Further, the ionic liquid includes a cation and an anion.
Further, the cation includes any one or a combination of two or more of imidazolium salt ion, pyridinium salt ion, piperidinium salt ion, pyrrolium salt ion, morpholinium salt ion and quaternary phosphonium salt ion, but is not limited thereto.
Further, the anion includes any one or a combination of two or more of halide, nitrate, tetrafluoroborate, triflate, acetate, p-toluenesulfonate, diethyl ester and methyl ester ions, but is not limited thereto.
For example, specifically, the ionic liquid may be 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate, 1-hydroxyethyl-3-methylimidazolium nitrate, 1-butyl-3-methylpiperidine hexafluorophosphate, N-pyridyl-trifluoromethanesulfonate, or the like.
In a preferred embodiment, the organic compound includes any one or a combination of two or more of an organic semiconductor compound having a planar molecular structure, fullerene, and a derivative thereof, but is not limited thereto.
Preferably, the organic compound includes a fused aromatic organic semiconductor compound.
Further, the fused ring aromatic organic semiconductor compound includes any one or a combination of two or more of acene compounds, metal phthalocyanine compounds, perylenes, perylene imide derivatives, perylene anhydride compounds, tetrafluoro-p-benzoquinone dimethane metal compounds, metalloporphyrin compounds, rubrene, and N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, but is not limited thereto.
For example, specifically, the fused aromatic organic semiconductor compound may be octaethylporphyrin copper, nickel phthalocyanine, fullerene (C60), pentacene, or the like.
In a preferred embodiment, the preparation method further comprises: and stripping the organic self-supporting film on the surface of the liquid phase system.
Further, the preparation method further comprises the following steps: and collecting the organic self-supporting film obtained by surface stripping of the liquid-phase system by using a collecting device. The size and the shape of the organic self-supporting film can be regulated and controlled by regulating the size and the shape of the collecting device.
The embodiment of the invention also provides the application of the organic self-supporting film in the preparation of organic semiconductor devices.
In summary, the preparation method of the invention adopts a physical vapor deposition technology with liquid as a substrate, is suitable for any organic small molecule, does not need to modify and recombine the organic small molecule, and uses the green ionic liquid which has recycling property. Therefore, the method has the advantages of wide application range, simplicity in operation, environmental friendliness, energy conservation and the like, and has a very important promoting effect on really realizing the preparation of large-area organic semiconductor devices.
In addition, by the technical scheme of the invention, the obtained organic self-supporting film has good crystallinity, transferability and excellent compatibility, the self-supporting film is of a planar two-dimensional network structure, all organic nanocrystals can be directly contacted with a target substrate, and the defects that the traditional organic film is difficult to separate and is not well contacted with the target substrate, so that the application of the organic film is influenced can be overcome.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
In the following examples, the methods used are conventional methods unless otherwise specified.
Example 1
5mg of the organic compound was placed in one end of a tube furnace in a PVD system, 3ml of an ionic liquid was placed in the other end of the tube furnace, and the organic compound was heated to 325 ℃ at 100ppm N2Depositing for 60min under the action of carrier gas to obtain continuous organic self-supporting film in certain size on the surface of the ionic liquid. Please refer to fig. 1 for the experimental apparatus and process. In this example, the organic compound selected was copper octaethylporphyrin and the ionic liquid selected was 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate.
The organic self-supporting film obtained in this example had a rectangular shape of 6cm × 1cm in external dimensions, and as shown in fig. 2, the film had a thickness of 2 μm, a microstructure of a two-dimensional planar cross-linked fishing net structure composed of nanobelts 20 μm long and 100nm wide, and a pore structure of 2 μm, as shown in fig. 4. The organic self-supporting film has excellent crystallinity and growth orientation, see fig. 5. In addition. The organic self-supporting film can be transferred to solid surfaces such as silicon, quartz, glass plates, etc., or can be transferred to a surface of deionized water, as shown in FIGS. 3 a-3 b. After the organic self-supporting film is transferred to the surface of the silicon substrate, the organic self-supporting film is soaked in an ethanol solution for 10 days, and no shedding phenomenon occurs.
Example 2
10mg of the organic compound was placed in one end of a tube furnace in a PVD system, 3ml of an ionic liquid was placed in the other end of the tube furnace, and the organic compound was heated to 550 ℃ at 100ppm N2Depositing for 30min under the action of carrier gas to obtain the ion liquid surface with certain sizeA self-supporting membrane. The experimental setup and procedure are shown in FIG. 1. In this example, the organic compound selected was nickel phthalocyanine and the ionic liquid selected was 1-hydroxyethyl-3-methylimidazole nitrate.
The organic self-supporting film obtained in this example had a rectangular shape with an external dimension of 3cm × 1cm, the film thickness was 100nm, the microstructure was a two-dimensional planar cross-linked fishing net structure composed of nanotubes with an inner diameter of 5nm, an outer diameter of 10nm, and a length of 200 μm, and the pore structure was 5nm, see fig. 7. The organic self-supporting film has good crystallinity and growth orientation. In addition, the organic self-supporting film can be transferred to the surface of solid such as silicon, quartz, glass plate, etc., or can be transferred to the surface of deionized water, and the drawings are similar to those of fig. 3 a-3 b. After the organic self-supporting film is transferred to the surface of the silicon substrate, the organic self-supporting film is soaked in an acetone solution for 30 days, and no shedding phenomenon occurs.
Example 3
6mg of the organic compound was placed in one end of a tube furnace in a PVD system, 3ml of an ionic liquid was placed in the other end of the tube furnace, and the tube furnace was heated to 355 ℃ at the end where the organic compound was placed, at 100ppmN2Depositing for 80min under the action of carrier gas to obtain the organic self-supporting film with certain size on the surface of the ionic liquid. Please refer to fig. 1 for the experimental apparatus and process. In this example, the organic compound selected was zinc octaethylporphyrin and the ionic liquid selected was N-pyridyl-triflate.
The appearance size of the organic self-supporting film obtained in this example is a circle with a diameter of about 2.5cm, the film thickness is 4 μm, the microstructure is a two-dimensional plane cross-linked fishing net structure composed of nanobelts with a length of 100 μm and a width of 1000nm, the pore structure is 5 μm, and the similar to fig. 4 is obtained. The organic self-supporting film has good crystallinity and growth orientation. In addition. The organic self-supporting film can be transferred to solid surfaces such as silicon, quartz, glass plate, etc., or to a surface of deionized water, similar to fig. 3 a-3 b. After the organic self-supporting film is transferred to the surface of the silicon substrate, the organic self-supporting film is soaked in water for 20 days, and no shedding phenomenon occurs.
Example 4
Placing 2mg of organic compound in POne end of the tube furnace in the VD System, 3ml of the ionic liquid was placed in the other end of the tube furnace, and the tube furnace was heated to 500 ℃ at 100ppmN2Depositing for 10min under the action of carrier gas to obtain the organic self-supporting film with certain size on the surface of the ionic liquid. The experimental setup and procedure are shown in FIG. 1. In this example, the organic compound selected was fullerene (C60) and the ionic liquid selected was 1-butyl-3 methylpiperidine hexafluorophosphate.
The organic self-supporting film obtained in this example had an appearance size of a circle having a diameter of about 3cm, a film thickness of 100nm, a microstructure of a two-dimensional planar cross-linked fishing net structure composed of nanowires 10 μm long and having a diameter of 80nm and nanotubes having an inner diameter of 20nm, an outer diameter of 80nm and a length of 1000 μm, and a pore structure of 50 μm, see fig. 8. The organic self-supporting film has good crystallinity and growth orientation. In addition, the organic self-supporting film can be transferred to the surface of solid such as silicon, quartz, glass plate, etc., or can be transferred to the surface of deionized water, and the drawings are similar to those of fig. 3 a-3 b. After the organic self-supporting film is transferred to the surface of the silicon substrate, the organic self-supporting film is soaked in water for 60 days, and no shedding phenomenon occurs.
Example 5
30mg of the organic compound was placed in one end of a tube furnace in a PVD system, 3ml of an ionic liquid was placed in the other end of the tube furnace, and the tube furnace was heated to 325 ℃ at the end where the organic compound was placed, at 100ppmN2Depositing for 240min under the action of carrier gas to obtain the organic self-supporting film with certain size on the surface of the ionic liquid. The experimental setup and procedure are shown in FIG. 1. In this example the organic compound selected was pentacene and the ionic liquid selected was N-pyridyl-triflate.
The organic self-supporting film obtained in this example had an appearance size of a circle having a diameter of about 3cm, a film thickness of 50 μm, a microstructure of a two-dimensional planar cross-linked fishing net structure composed of nanotubes having an inner diameter of 30nm, an outer diameter of 100nm, and a length of 800 μm, and a pore structure of 20 μm, as shown in FIG. 9. The organic self-supporting film has good crystallinity and growth orientation. In addition, the organic self-supporting film can be transferred to the surface of solid such as silicon, quartz, glass plate, etc., or can be transferred to the surface of deionized water, and the drawings are similar to those of fig. 3 a-3 b. After the organic self-supporting film is transferred to the surface of a PET substrate, the organic self-supporting film is strongly twisted for 300 times, and no peeling phenomenon occurs.
Example 6
20mg of the organic compound was placed in one end of a tube furnace in a PVD system, 5ml of an ionic liquid was placed in the other end of the tube furnace, and the tube furnace was heated to 350 ℃ at the end where the organic compound was placed, at 100ppmN2Depositing for 90min under the action of carrier gas to obtain the organic self-supporting film with certain size on the surface of the ionic liquid. The experimental setup and procedure are shown in FIG. 1. In this example, the organic compound selected was cobalt phthalocyanine, and the ionic liquid selected was 1-butyl-3 methylpiperidine hexafluorophosphate.
The organic self-supporting film obtained in this example had a rectangular shape of 5cm × 2cm in appearance, a film thickness of 300nm, a microstructure of a two-dimensional planar cross-linked fishing net structure composed of 1 μm long nanowires having a diameter of 5nm, and a pore structure of 500nm, as shown in fig. 10. The organic self-supporting film has good crystallinity and growth orientation. In addition, the organic self-supporting film can be transferred to the surface of solid such as silicon, quartz, glass plate, etc., or can be transferred to the surface of deionized water, and the drawings are similar to those of fig. 3 a-3 b. After the organic self-supporting film is transferred to the surface of the silicon substrate, the organic self-supporting film is soaked in an acetone solution for 20 days, and no shedding phenomenon occurs.
Example 7
80mg of the organic compound was placed in one end of a tube furnace in a PVD system, 10ml of an ionic liquid was placed in the other end of the tube furnace, and the organic compound was heated to 625 ℃ at 300ppmN2Depositing for 320min under the action of carrier gas to obtain the organic self-supporting film with certain size on the surface of the ionic liquid. The experimental setup and procedure are shown in FIG. 1. In this example, the organic compound selected was pentacene and the ionic liquid selected was 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate.
The appearance size of the organic self-supporting film obtained in this example is a circle with a diameter of about 8cm, the film thickness is 100 μm, the microstructure is a two-dimensional plane cross-linked fishing net structure composed of nanobelts with a length of 500nm and a width of 50nm, and the pore structure is 80nm, which is similar to that in fig. 9. The organic self-supporting film has good crystallinity and growth orientation. In addition, the organic self-supporting film can be transferred to the surface of solid such as silicon, quartz, glass plate, etc., or can be transferred to the surface of deionized water, and the drawings are similar to those of fig. 3 a-3 b. After the organic self-supporting film is transferred to the surface of a PET substrate, the organic self-supporting film is strongly twisted for 500 times, and no peeling phenomenon occurs.
Example 8
12mg of the organic compound was placed in one end of a tube furnace in a PVD system, 8ml of an ionic liquid was placed in the other end of the tube furnace, and the tube furnace was heated to 485 ℃ at 200ppmN2Depositing for 90min under the action of carrier gas to obtain the organic self-supporting film with certain size on the surface of the ionic liquid. Please refer to fig. 1 for the experimental apparatus and process. In this example, the organic compound selected was octaethylporphyrin platinum, and the ionic liquid selected was 1-butyl-3 methylpiperidine hexafluorophosphate.
The organic self-supporting film obtained in this example had an appearance size of a circle having a diameter of about 4cm, a film thickness of 80 μm, a microstructure of a two-dimensional planar cross-linked fishing net structure composed of nanobelts 40 μm long and 250nm wide and nanotubes 50nm in inner diameter, 100nm in outer diameter and 1000 μm in length, and a pore structure of 10 μm, as shown in fig. 11. The organic self-supporting film has good crystallinity and growth orientation. In addition. The organic self-supporting film can be transferred to solid surfaces such as silicon, quartz, glass plate, etc., or to a surface of deionized water, similar to fig. 3 a-3 b. After the organic self-supporting film is transferred to the surface of the silicon substrate, the organic self-supporting film is soaked in ethanol for 30 days, and no shedding phenomenon occurs.
Through the embodiments 1 to 8, it can be found that the above technical scheme of the present invention adopts the physical vapor deposition technology using liquid as a substrate, is suitable for any small organic molecule, does not need any modification and recombination on the small organic molecule, and the used ionic liquid is a green solvent, and has recyclability. Therefore, the method has the advantages of wide application range, simplicity in operation, environmental friendliness, energy conservation and the like, and has a very important promoting effect on really realizing the preparation of large-area organic semiconductor devices.
In addition, the present inventors have also conducted experiments with other raw materials and conditions and the like listed in the present specification with reference to the manner of example 1 to example 8, and have also produced an organic self-supporting film having excellent crystallinity, transferability and excellent compatibility.
It should be understood that the above describes only some embodiments of the present invention and that various other changes and modifications may be affected therein by one of ordinary skill in the related art without departing from the scope or spirit of the invention.

Claims (24)

1. An organic self-supporting film characterized by: the organic self-supporting film comprises a two-dimensional fishing net structure, the fishing net structure comprises a net rack and a plurality of fishing net mesh-shaped hole structures formed in the net rack, the net rack is formed by interweaving any one or combination of more than two of a plurality of one-dimensional nanowires, nanobelts and nanotubes, and the nanowires, the nanobelts and the nanotubes are all formed by organic nanocrystals;
and, the method for preparing the organic self-supporting film includes: heating the organic compound to sublimation by adopting a physical vapor deposition method, and continuously depositing the organic compound on the surface of a liquid phase system by utilizing carrier gas to form a continuous organic self-supporting film; the density of the liquid phase system is greater than that of the organic compound, and the organic compound is insoluble in the liquid phase system, wherein the deposition time is 10-320 min, the deposition temperature is 325-625 ℃, the air flow rate of the carrier is 100-300 ppm, the liquid phase system comprises an ionic liquid, the ionic liquid comprises cations and anions, the cations are selected from any one or combination of more than two of imidazolium salt ions, pyridinium salt ions, piperidinium salt ions, pyrrolate salt ions, morpholinium salt ions and quaternary phosphonium salt ions, and the anions are selected from any one or combination of more than two of halogen ions, nitrate radicals, tetrafluoroborate radicals, trifluoromethanesulfonate radicals, acetate radicals, p-toluenesulfonate radicals, diethyl radicals and methyl ester radicals.
2. The organic free standing film of claim 1, wherein: the cross section of the nanowire is 5-100 nm, and the length of the nanowire is 1-1000 mu m.
3. The organic free standing film of claim 1, wherein: the width of the nano-belt is 50-1000 nm, and the length of the nano-belt is 500 nm-100 mu m.
4. The organic free standing film of claim 1, wherein: the nanotube has an inner diameter of 5 to 50nm, an outer diameter of 10 to 100nm, and a length of 1 to 1000 μm.
5. The organic free standing film of claim 1, wherein: the thickness of the organic self-supporting film is 100 nm-100 mu m.
6. The organic free standing film of claim 1, wherein: the organic self-supporting film comprises a planar two-dimensional fishing net structure.
7. The organic free standing film of claim 1, wherein: the fishing net structure comprises a plurality of periodic fishing net units which are connected with each other.
8. The organic free standing film of claim 7, wherein: 1-100 fishing net units are arranged in a 1-100 mu m fishing net structure.
9. The organic free standing film of claim 1, wherein: the fishing net structure comprises a regular structure and/or an irregular structure.
10. The organic free standing film of claim 9, wherein: the net frame in the regular structure is formed by the combination of any one or more than two of a plurality of one-dimensional nanowires, nanobelts and nanotubes which are arranged vertically and horizontally.
11. The organic free standing film of claim 9, wherein: in the irregular structure, any one or more combinations of the one-dimensional nanowires, the nanobelts and the nanotubes mutually form a set angle arrangement.
12. The organic free standing film of claim 1, wherein: the net racks of the fishing net structure are all on the same plane.
13. The organic free standing film of claim 1, wherein: the size of the pore structure is 5 nm-50 μm.
14. The organic free standing film of claim 1, wherein: the organic nanocrystal is composed of an organic compound selected from any one or a combination of two or more of an organic semiconductor compound having a planar molecular structure, fullerene and a derivative thereof.
15. The organic free standing film of claim 14, wherein: the organic compound is selected from fused ring aromatic organic semiconductor compounds.
16. The organic free standing film of claim 15, wherein: the condensed-ring aromatic organic semiconductor compound is selected from any one or combination of more than two of acene compounds, metal phthalocyanine compounds, perylene imide derivatives, perylene anhydride compounds, tetrafluoro-p-benzoquinone dimethane metal compounds, metalloporphyrin compounds, rubrene and N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine.
17. The organic free standing film of claim 1, wherein: the organic self-supporting film is also bonded to a solid substrate or a liquid substrate.
18. The organic free standing film of claim 17, wherein: the solid substrate is selected from any one of silicon wafer, glass, PET, paper, aluminum foil, quartz plate, mica, fiber, copper plate, gold plate and silver plate.
19. The organic free standing film of claim 17, wherein: the liquid substrate includes all liquids that are immiscible with the organic compound.
20. The organic free standing film of claim 19, wherein: the liquid substrate is selected from any one or the combination of more than two of organic solvent, water and ionic liquid.
21. The organic free standing film of claim 1, wherein: the carrier gas comprises nitrogen.
22. The organic self-supporting film according to claim 1, wherein the method for preparing the organic self-supporting film further comprises: and stripping the organic self-supporting film on the surface of the liquid phase system.
23. The organic self-supporting film according to claim 22, wherein the method of preparing the organic self-supporting film further comprises: and collecting the organic self-supporting film obtained by surface stripping of the liquid-phase system by using a collecting device.
24. Use of the organic self-supporting film according to any one of claims 1 to 23 for the preparation of an organic semiconductor device.
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