CN102867917A - Flexible film used for flexible organic solar battery - Google Patents

Abstract

A flexible film for flexible organic solar cells. The invention provides a transparent conductive film on one side of a flexible transparent substrate, and sequentially arranges a barrier layer and a functional layer on the other side of the flexible transparent substrate. The functional layer consists of To the outside are the organic fluororesin layer and the organic-inorganic hybrid layer. The flexible film of the invention is resistant to ultraviolet light, heat and humidity, and has high surface hardness, and can significantly improve the service life of the battery when used for making flexible organic solar cells.

Description

A flexible film for flexible organic solar cells

technical field

The invention relates to the technical field of solar cells, in particular to a flexible film used for flexible organic solar cells.

Background technique

The conversion efficiency of third-generation organic solar cells is still low compared with that of crystalline silicon. However, the growth rate of its conversion efficiency in the last three years or so is the fastest among many technologies of solar cells. The highest conversion efficiency in 2009 was just over 6%. Recently, Japan’s Mitsubishi Chemical and the University of California, Los Angeles (UCLA) raised the conversion efficiency to over 10%. Recently, German solar cell manufacturer Heliatek has created a conversion efficiency as high as 10.7%. (effective area 1.1cm ² ) world record.

Compared with inorganic crystalline silicon solar cells, organic solar cells have another problem that needs to be solved urgently in addition to low conversion efficiency, that is, poor stability and short life. This is mainly due to the fact that organic semiconductor active materials and electrode materials are susceptible to external environment. Effects of water, oxygen, etc. Oxygen itself is a triplet quencher, which will oxidize the organic semiconductor material in the active layer, resulting in the opening of unsaturated bonds, resulting in a significant decrease in the quantum efficiency of luminescence; oxygen will also oxidize active metal electrodes with low work functions, resulting in a decrease in electron transport capability; Water vapor easily causes the organic semiconductor in the active layer to undergo hydrolysis reaction, and also corrodes the hole transport layer to cause the surface degradation of the ITO anode.

For the impact of the external environment, encapsulation technology is usually used to prevent water and oxygen in the air from entering the device and reacting with the film. Currently commonly used packaging flexible organic solar cell device structure: barrier film/encapsulation glue or film/organic solar cell element/encapsulation glue or film/barrier film, wherein the barrier film and organic solar cell element are respectively used to make barriers on flexible substrates layer and transparent anode/organic active layer/opaque metal cathode. The organic solar cell device formed by this structure, because both the barrier film and the transparent anode in the organic solar cell element use a flexible substrate (the transmittance is less than 93%), which greatly reduces the impact of the organic active layer on sunlight. The absorption and utilization of flexible organic solar cell devices further reduce the photoelectric conversion efficiency after encapsulation. Japanese patent JP2008-21605 discloses a new structural flexible film used in the display field: a conductive layer and a barrier layer are respectively formed on both sides and the same side of the flexible substrate. Although the flexible film of this structure reduces a layer of flexible substrate, increases the light transmittance, and saves costs, but due to the lack of coatings such as UV resistance, heat and humidity resistance, and hardening, the weather resistance is poor and the surface hardness of the barrier layer is low. Flexible organic solar cells assembled with it have a short lifespan.

Contents of the invention

The technical problem to be solved in the present invention is to provide a flexible film with UV resistance, heat and humidity resistance, and high surface hardness for the above-mentioned existing problems in packaging flexible organic solar cell devices, and to apply the film to flexible organic solar cells. Can effectively improve battery life.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

A flexible film for flexible organic solar cells, a transparent conductive film is provided on one side of a flexible transparent substrate, and a barrier layer and a functional layer are sequentially provided on the other side of the flexible transparent substrate, and the functional layer is arranged from the inside to the outside It is an organic fluororesin layer and an organic-inorganic hybrid layer in sequence.

In the above flexible film, the organic fluorine resin layer in the functional layer is one of perfluoroethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer, and polychlorotrifluoroethylene.

In the above flexible film, the organic fluororesin layer in the functional layer has a thickness of 0.1-30 μm.

In the above flexible film, the organic component in the organic-inorganic hybrid layer in the functional layer is one of acrylic resin, polyethylene, and silicone polymer.

In the above flexible film, the inorganic component in the organic-inorganic hybrid layer in the functional layer is one or both of nanoscale TiO ₂ , ZnO and CeO ₂ particles.

In the above flexible film, the mass ratio of the organic component to the inorganic component in the organic-inorganic hybrid layer in the functional layer is 10:1˜1:5.

In the above flexible film, the film thickness of the organic-inorganic hybrid layer in the functional layer is 0.1-50 μm.

In the above flexible film, the water vapor transmission rate of the flexible film is 10 ^-3 g/m ² ·24h or less, and the oxygen transmission rate is 10 ^-3 cc/m ² ·24h·atm or less.

In the above flexible film, the sheet resistance of the flexible film is 0.1-150Ω/□; the light transmittance of the flexible film is above 75%.

Compared with the prior art, since the flexible film of the present invention is provided with a functional layer, it not only has conductivity, water and oxygen resistance, but also has high surface hardness, ultraviolet resistance, and heat and humidity resistance, and is used for making flexible organic solar cells. Can significantly improve battery life.

In the flexible film of the present invention, a transparent conductive film is provided on one side of the flexible transparent substrate; a transparent barrier layer and a functional layer are provided on the other side, and the functional layer is an organic fluororesin layer and an organic-inorganic hybrid layer from inside to outside. .

The flexible transparent substrate suitable for the present invention requires a certain heat resistance. If the thermal expansion size of the flexible transparent substrate and the inorganic barrier layer are inconsistent under high temperature environment, it will lead to cracking and peeling of the inorganic barrier layer. Therefore, the flexible transparent substrate of the present invention selects a resin film with a small linear expansion coefficient, preferably less than 40ppm/°C, such as polyethylene naphthalate (PEN), polycarbonate (PC), polyacrylate (PAR), Any one of polyethersulfone (PES), polysulfone (PSF), polyimide (PI), polyethylene terephthalate (PET), preferably polyparaffin with low price and excellent performance Ethylene phthalate PET. The thickness of the flexible transparent substrate 21 is 12-200 μm. If it is too thin, the mechanical strength of the substrate will be too low, which is not conducive to the production of conductive films, barrier layers and functional layers; if it is too thick, the transmittance will be too low and the flexibility will also become Difference.

The transparent conductive film is arranged on the surface of the flexible transparent substrate. The transparent conductive film suitable for the present invention may be a film with a surface resistance of less than 200Ω/□ and a transparency greater than 70%. The transparent conductive film suitable for the present invention is selected from one of conductive oxide films, conductive polymer films, and metal grids. Among them, the conductive oxide film is selected from one of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO) and gallium-doped zinc oxide (GZO) films; conductive polymer The material film is selected from one of polythiophene, polyaniline and polyacetylene films; the metal grid conductive film is selected from metal grids with excellent conductivity such as silver, copper or their mixtures. Among them, since the metal grid has excellent electrical conductivity and high transparency, the present invention preferably uses the metal grid transparent electrode. The preparation method of the transparent conductive oxide is any one of the known magnetron sputtering method, ion sputtering method, resistive evaporation method, and atomic layer deposition method; the preparation method of the conductive polymer is the known spin coating method , micro gravure coating method, screen printing method, inkjet printing method, doctor blade coating method; the preparation method of the metal grid is the well-known magnetron sputtering method, etching method, silver salt method, mesh Any one of grid weaving method and inkjet printing method. The thickness of the metal wires in the metal grid transparent conductive film is 0.1-1 μm, the width is 5-100 μm, and the spacing is 0.1-5 mm. The open porosity of the metal grid transparent conductive film is greater than or equal to 70%, preferably greater than or equal to 80%, more preferably greater than or equal to 90%.

The barrier layer is an organic-inorganic alternate lamination composite structure, which is arranged on the other surface of the flexible transparent substrate to form two or more pairs of organic-inorganic laminations. For the inorganic barrier layer, the gas barrier is mainly achieved by forming a dense metal or metal compound particle stack structure and reducing the particle gap. The inorganic barrier layer suitable for the present invention may be a thin film formed from any one of aluminum oxide, silicon oxide, a mixture of aluminum oxide and silicon oxide, silicon nitride, silicon oxycarbide, and silicon oxynitride. The formation method of the inorganic barrier layer film in the present invention can be selected from magnetron sputtering method, ion sputtering method, resistive evaporation method, plasma enhanced chemical vapor deposition method (PECVD), electron beam physical vapor deposition method (EBPVD) 1. Any one of atomic layer deposition (ALD), PECVD is preferred, the deposition process has low basic temperature, fast rate, good film quality, less pinholes, and is not easy to crack. The film thickness of the transparent inorganic barrier layer of the present invention is 10-300nm, preferably 20-200nm, more preferably 30-120nm, too thick or too thin will affect its barrier performance. If the inorganic barrier layer is too thin, the film will not be dense enough, and there will be pinhole defects, resulting in low barrier properties; if the film layer is too thick, it will cause the film to bend and crack, etc., resulting in a significant drop in barrier properties. The organic layer is coated on the surface of the transparent inorganic barrier layer. As a planarization layer, it can smooth and fill defects such as pinholes and cracks in the inorganic barrier layer to form a dense structure. Since the inorganic barrier layer inevitably has defects such as pinholes, cracks, and protrusions during the production process, the gas can pass directly through the capillary flow, and the barrier property drops sharply. Improve the barrier properties of the film. The organic layer suitable for the present invention can be selected from any film formed in polyurethane resin, polyester resin, epoxy resin, silicone resin, and the coating method is doctor blade coating method, screen printing method, spray coating method . One of the micro gravure coating methods, the coating thickness is 0.1-30 μm, preferably 0.2-15 μm, more preferably 0.3-10 μm. If the organic layer is too thin, it cannot completely cover the defects of the inorganic barrier layer; if it is too thick, the solar light transmittance will be reduced.

The functional layer is arranged on the surface of the barrier layer, and consists of an organic fluororesin layer and an organic-inorganic hybrid layer from inside to outside. The organic fluorine resin layer is coated on the surface of the barrier layer, which can further improve the water and oxygen barrier properties of the film, and at the same time greatly improve the weather resistance, heat and humidity resistance, electrical insulation properties and mechanical properties of the film. The performance of fluororesin is controlled by two main factors, that is, the high electronegativity and small atomic radius of fluorine atoms. The 2s and 2p orbitals of fluorine atoms are particularly matched with the corresponding orbitals of carbon atoms. The above reasons also lead to the particularly low electronegativity of fluorine atoms polarizability. Generally, the carbon chain of polyolefin molecules is zigzag. After fluorine atoms replace hydrogen atoms, due to the high electronegativity of fluorine atoms and the mutual repulsion of adjacent fluorine atoms, the C-C-C bond angle of the main chain changes from 120° to 107°. Arranged in a spiral so that the carbon chain is surrounded by fluorine atoms. The intermolecular cohesion of fluorocarbons is low, the surface free energy is low, it is difficult to be infiltrated or adhered by liquid or solid, and the surface friction coefficient is small, which makes fluorocarbon resins have many excellent properties. The organic fluorine resin layer suitable for the present invention can be selected from any one of perfluoroethylene propylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), and polychlorotrifluoroethylene (PCTFE), preferably ETFE. The film thickness of the organic fluororesin layer is 0.1 to 30 μm, preferably 0.2 to 15 μm, more preferably 0.3 to 10 μm.

The organic-inorganic hybrid layer is coated on the surface of the organic fluorine resin layer. The organic components suitable for the organic-inorganic hybrid layer of the present invention can increase the surface hardness and smoothness of the barrier layer, so it can be used as a top protection layer to prevent the flexible film from being worn and damaged by external forces during use and reduce its barrier properties. The organic component suitable for the organic-inorganic hybrid layer of the present invention is selected from any one of acrylic resin, polyethylene, and silicone polymer, preferably acrylic resin, because of its high surface hardness, good heat resistance and excellent transparency of the polymer . The inorganic components suitable for the organic-inorganic hybrid layer of the present invention have the function of shielding ultraviolet rays due to their high refraction and high photoactivity. The inorganic components suitable for the organic-inorganic hybrid layer of the present invention are selected from nanoscale titanium dioxide (TiO ₂ ), zinc oxide (ZnO) and cerium oxide (CeO ₂ ) particles, preferably nanoscale TiO ₂ and ZnO. The anti-ultraviolet ability and its mechanism of the inorganic components in the organic-inorganic hybrid layer of the present invention are related to their particle size: when the particle size is large, the blocking of ultraviolet rays is mainly based on reflection and scattering, and the ultraviolet rays in the medium-wave and long-wave regions are both Effective; as the particle size decreases, light can pass through the particle surface of nano-inorganic oxides, and the reflection and scattering of ultraviolet rays in the long-wave region are not obvious, while the absorption of ultraviolet rays in the medium-wave region is significantly enhanced. The suitable particle size of nanoscale TiO ₂ , ZnO and CeO ₂ particles in the present invention is 10-100 nm, preferably 20-50 nm. In the present invention, the mass ratio of organic components to inorganic components is 10:1 to 1:5, preferably 8:1 to 1:3, more preferably 5:1 to 1:2. If the content of organic components is too high, the ability to absorb ultraviolet rays Decrease; if the content of inorganic components is too high, the hardness of the coating will decrease. The coating method suitable for the organic-inorganic hybrid layer of the present invention is any one of the doctor blade coating method, screen printing method, spray coating method, and micro-gravure coating method, and the coating thickness is 0.1-50 μm, preferably 0.5-25 μm , more preferably 1 to 10 μm. If the film layer is too thin, firstly, the defects of the barrier layer cannot be completely compensated; secondly, the surface hardness of the coating is low, and the purpose of protecting the inorganic barrier layer from damage cannot be achieved; thirdly, the incidence of ultraviolet rays cannot be completely blocked. If the film layer is too thick, it will reduce the sunlight transmittance.

The water vapor transmission rate of the flexible film obtained by the present invention is 10 ^-3 g/m ² ·24h or less, the oxygen transmission rate is 10 ^-3 cc/m ² ·24h ·atm or less, preferably the water vapor transmission rate is 10 ^-4 g/m ² ·24h or less, and the oxygen transmission rate is 5×10 ^-4 cc/m ² ·24h·atm or less.

The sheet resistance of the transparent conductive film of the flexible film produced above is 0.1-150Ω/□, preferably 0.1-60Ω/□, more preferably 0.1-15Ω/□.

The light transmittance of the above-mentioned flexible film is generally above 75%, preferably above 80%, more preferably above 85%.

Description of drawings

Fig. 1 is the structural representation of product of the present invention.

The symbols in the figure are represented as: 1-transparent conductive film; 2-flexible transparent substrate; 3-barrier layer; 4-functional layer; 41-organic fluororesin layer; 42-organic-inorganic hybrid layer.

Detailed ways

The flexible film for flexible organic solar cells provided by the present invention will be described in detail below in conjunction with the examples, but the protection scope of the present invention is not limited thereto.

Example 1

Preparation of transparent conductive film:

A PET substrate with a thickness of 125 μm was selected, and an indium tin oxide (ITO) transparent conductive film was fabricated on one side by magnetron sputtering method, with a sheet resistance of 31.8Ω/□.

Preparation of the barrier layer:

On the other side of the above-mentioned PET substrate, a 30nm-thick silicon oxide inorganic barrier layer was first prepared by plasma-enhanced chemical vapor deposition (PECVD), and then coated with a polyurethane resin binder on the surface, and dried to obtain a thickness of 5.1 μm organic barrier layer, and then alternately make two pairs of silicon oxide layers and polyurethane resin layers according to the above conditions to obtain a barrier layer.

Preparation of functional layer:

On the surface of the barrier layer prepared above, a layer of ethylene-tetrafluoroethylene copolymer (ETFE) was first coated with a thickness of 8.4 μm; then an organic-inorganic mixture was coated on the surface, the organic component was acrylic resin, and the inorganic component was titanium dioxide ( TiO ₂ ), the mass ratio of the two was 5:1, and an organic-inorganic hybrid layer with a film thickness of 3.6 μm was prepared.

The water vapor transmission rate of the flexible film prepared above is 9.3×10 ^-4 g/m ² ·24h, the oxygen transmission rate is 1.2×10 ^-3 cc/m ² ·24h·atm, and the light transmittance is 83.1%. .

The flexible film prepared above is used to assemble flexible organic solar cells, and the packaged device structure is the flexible film (functional layer/barrier layer/substrate/transparent conductive film)/ZnO/P3HT:PC ₆₁ BM/MoO ₃ / Al/EVA/barrier film.

Example 2

Preparation of transparent conductive film:

A PC substrate with a thickness of 75 μm was selected, and a silver metal grid transparent conductive film was fabricated on one side by inkjet printing method, and the sheet resistance was 2.1Ω/□.

Preparation of the barrier layer:

On the other side of the above-mentioned PC substrate, a 50nm-thick silicon oxynitride inorganic barrier layer was first prepared by electron beam physical vapor deposition (EBPVD), and then a polyester resin binder was coated on the surface, and after drying, a thickness of 3.5 μm organic barrier layer, and then alternately fabricate two pairs of silicon oxynitride layers and polyester resin layers according to the above conditions to obtain a barrier layer.

Preparation of functional layer:

On the surface of the barrier layer prepared above, a layer of perfluoroethylene propylene copolymer (FEP) is first coated with a thickness of 2.4 μm; then an organic-inorganic mixture is coated on the surface, the organic component is polyethylene, and the inorganic component is zinc oxide ( ZnO), the mass ratio of the two is 3:1, and an organic-inorganic hybrid layer with a film thickness of 7.2 μm is obtained.

The water vapor transmission rate of the flexible film prepared above is 6.1×10 ^-4 g/m ² ·24h, the oxygen transmission rate is 7.9×10 ^-4 cc/m ² ·24h·atm, and the light transmittance is 80.5%. .

The flexible thin film prepared above was used to assemble flexible organic solar cells, and the structure of the packaged device was the same as that in Example 1.

Example 3

Preparation of transparent conductive film:

A PEN substrate with a thickness of 175 μm was selected, and a polythiophene transparent conductive film was fabricated on one side by micro-gravure coating method, with a sheet resistance of 61.8Ω/□.

Preparation of the barrier layer:

On the other side of the above-mentioned PEN substrate, a 70nm-thick silicon carbide inorganic barrier layer was first produced by magnetron sputtering, and then an epoxy resin adhesive was coated on the surface, and an organic barrier layer with a thickness of 8.5 μm was obtained after drying. barrier layer, and then alternately fabricate two pairs of silicon oxycarbide layers and epoxy resin layers according to the above conditions to obtain a barrier layer.

Preparation of functional layer:

On the surface of the barrier layer prepared above, a layer of ethylene-tetrafluoroethylene copolymer (ETFE) is first coated with a thickness of 5.9 μm; then an organic-inorganic mixture is coated on the surface, the organic component is a silicone polymer, and the inorganic component is Cerium dioxide (CeO ₂ ), the mass ratio of the two was 1:1, and an organic-inorganic hybrid layer with a film thickness of 7.2 μm was prepared.

The water vapor transmission rate of the flexible film prepared above is 4.1×10 ^-4 g/m ² ·24h, the oxygen transmission rate is 8.5×10 ^-4 cc/m ² ·24h·atm, and the light transmittance is 80.9%. .

The flexible thin film prepared above was used to assemble flexible organic solar cells, and the structure of the packaged device was the same as that in Example 1.

Example 4

Preparation of transparent conductive film:

A PET substrate with a thickness of 115 μm was selected, and a fluorine-doped tin oxide (FTO) transparent conductive film was fabricated on one side by magnetron sputtering method, with a sheet resistance of 17.9Ω/□.

Preparation of the barrier layer:

On the other side of the above-mentioned PET substrate, a 90nm-thick aluminum oxide inorganic barrier layer was first produced by atomic layer deposition (ALD), and then coated with a silicone resin binder on the surface, and dried to obtain a thickness of 3.5μm. Organic barrier layer, and then alternately fabricate two pairs of aluminum oxide layers and silicone resin layers according to the above conditions to obtain a barrier layer.

Preparation of functional layer:

On the surface of the barrier layer prepared above, a layer of perfluoroethylene propylene copolymer (FEP) was first coated with a thickness of 9.8 μm; then an organic-inorganic mixture was coated on the surface, the organic component was polyethylene, and the inorganic component was zinc oxide ( ZnO), the mass ratio of the two is 1:2, and an organic-inorganic hybrid layer with a film thickness of 3.2 μm is obtained.

The water vapor transmission rate of the flexible film prepared above is 3.5×10 ^-3 g/m ² ·24h, the oxygen transmission rate is 4.9×10 ^-3 cc/m ² ·24h·atm, and the light transmittance is 82.5%. .

The flexible thin film prepared above was used to assemble flexible organic solar cells, and the structure of the packaged device was the same as that in Example 1.

Example 5

Preparation of transparent conductive film:

A PI substrate with a thickness of 175 μm was selected, and a polyaniline transparent conductive film was fabricated on one side by the screen printing method, and the sheet resistance was 82.3Ω/□.

Preparation of the barrier layer:

On the other side of the above-mentioned PEN substrate, a 119nm-thick silicon carbide inorganic barrier layer was first produced by ion sputtering, and then a polyurethane resin binder was coated on the surface, and an organic barrier layer with a thickness of 9.7 μm was obtained after drying. , and then alternately make two pairs of silicon carbide layers and polyurethane resin layers according to the above conditions to obtain a barrier layer.

Preparation of functional layer:

On the surface of the barrier layer prepared above, a layer of ethylene-tetrafluoroethylene copolymer (ETFE) is first coated with a thickness of 3.1 μm; then an organic-inorganic mixture is coated on the surface, the organic component is a silicone polymer, and the inorganic component is A mixture of titanium dioxide and zinc oxide (1:1), the mass ratio of the two is 1:4, and an organic-inorganic hybrid layer with a film thickness of 9.9 μm is prepared.

The water vapor transmission rate of the flexible film prepared above is 3.1×10 ^-4 g/m ² ·24h, the oxygen transmission rate is 7.5×10 ^-4 cc/m ² ·24h·atm, and the light transmittance is 81.9%. .

The flexible thin film prepared above was used to assemble flexible organic solar cells, and the structure of the packaged device was the same as that in Example 1.

Comparative example 1:

Preparation of transparent conductive film: same as embodiment 1.

Preparation of barrier layer: same as Example 1.

The flexible thin film prepared above was used to assemble flexible organic solar cells, and the structure of the packaged device was the same as that in Example 1.

See Table 1 for the performance indexes of the flexible films prepared in Examples 1-5 and Comparative Example 1 for UV resistance, heat and humidity resistance, and surface hardness, as well as the service life of the assembled flexible organic solar cells.

(1) UV aging test conditions: UVB313 ultraviolet lamp is used as the light source, the light and condensation temperatures are 60°C and 40°C respectively, and the time is

4h, 4h, light and condensation alternately for a total of 4000h. The yellowing index (△YI) after UV aging resistance is tested according to GB2409-80 "Plastics Yellowness Index Test Method".

(2) Damp heat aging test

Conditions: Humidity 85RH%, temperature 85°C, time 1000h. The yellowing index (△YI) after damp heat aging resistance is tested according to GB2409-80 "Plastics Yellowness Index Test Method".

(3) Surface hardness test

According to the national GB/T6739-1996 standard, it is measured with a pencil hardness tester.

(4) Service life test of assembled flexible organic solar cells

Test conditions for photoelectric conversion efficiency of cells: XES-502S+ELS155 type AAA solar simulator of Japan SAN-EI Company, spectral distribution AM1.5G, light intensity 1000W/m ² , Keithly2400 type digital source meter for IV curve, temperature 25°C.

Battery service life test: Measured by the length of time it takes for the photoelectric conversion efficiency to decay above 20% under accelerated battery aging conditions (temperature 65°C, humidity 85RH%), 100h is equivalent to 1 year of natural storage of the battery.

Each embodiment of table 1 and comparative example data table

. It can be seen from the data in Table 1 that the flexible films invented in Examples 1, 2, 3, 4 and 5, compared with the flexible films without functional layers in Comparative Example 1, have obviously excellent resistance to ultraviolet rays and heat and humidity, and high surface hardness. 4 times longer battery life.

Claims (9)

1. fexible film that is used for flexible organic solar batteries, it is characterized in that, side at flexible and transparent base material (2) arranges nesa coating (1), opposite side at flexible and transparent base material (2) sets gradually barrier layer (3) and functional layer (4), and described functional layer (4) is followed successively by organic fluorine layer (41) and organic-inorganic mixed layer (42) from inside to outside.

2. described fexible film according to claim 1 is characterized in that, the organic fluorine layer (41) in the described functional layer (4) is a kind of in fluorinated ethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer, the polytrifluorochloroethylene.

3. described fexible film according to claim 2 is characterized in that the thickness of the organic fluorine layer (41) in the described functional layer (4) is 0.1～30 μ m.

4. described fexible film according to claim 3 is characterized in that, the organic principle in the organic-inorganic mixed layer (42) in the described functional layer (4) is a kind of in acrylic resin, polyethylene, the silicon-oxygen polymer.

5. described fexible film according to claim 4 is characterized in that, the inorganic constituents in the described functional layer (4) in the organic-inorganic mixed layer (42) is nanoscale TiO ₂, ZnO and CeO ₂In the particle one or both.

6. described fexible film according to claim 5 is characterized in that the organic principle in the organic-inorganic mixed layer (42) in the described functional layer (4) and the mass ratio of inorganic constituents are 10:1～1:5.

7. described fexible film according to claim 6 is characterized in that the thickness of the organic-inorganic mixed layer (42) in the described functional layer (4) is 0.1～50 μ m.

8. described fexible film according to claim 7 is characterized in that the moisture-vapor transmission of described fexible film is 10 ^-3G/m ²24h is following, OTR oxygen transmission rate is 10 ^-3Cc/m ²Below the 24hatm.

9. described fexible film according to claim 8 is characterized in that the square resistance of described fexible film is 0.1 ~ 150 Ω/; The light transmittance of described fexible film is more than 75%.

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