Flexible transparent conductive film, preparation method and application thereof, and perovskite battery

Abstract

The invention discloses a flexible transparent conductive film, a preparation method and application thereof, and a perovskite cell, and relates to the technical field of transparent conductive films. By adopting the structure of the multi-layer electrode layer, and the material of the metal oxide layer in the multi-layer electrode layer comprises oxides of at least three metals of Ti, Nb, Zn, Sn, In, W and Al, the metal oxide layer can be endowed with good conductivity and high light transmittance through multi-metal doping, and meanwhile, the defect of high brittleness of the metal oxide layer is overcome; the flexibility of the metal oxide layer is improved, and the use stability is ensured. Besides, by doping Bi, Pd, Cu, Nd, In, Sn, Sb and other metals in Ag of the metal layer, the three-dimensional growth trend of Ag can be inhibited, so that the metal layer can realize excellent conductivity with a relatively thin thickness, and the problem that conductivity and light transmission of the metal layer cannot be considered at the same time is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of transparent conductive films, in particular to a flexible transparent conductive film, a preparation method and application thereof, and a perovskite battery. BACKGROUND

[0002] A transparent conductive film is a material with both light transmission and conductivity, which is widely used in touch panels, flexible thin film photovoltaics and wearable display devices. However, traditional transparent conductive films such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO) and aluminum-doped zinc oxide (AZO) have poor conductivity and flexibility, and are high in brittleness. After long-term use, they are prone to cracking or peeling from the surrounding film layer due to repeated bending or thermal stress and other external factors.

[0003] The dielectric / metal / dielectric (DMD) multilayer electrode structure is considered as a potential alternative to the ITO electrode in flexible perovskite solar cells (PSC) due to its extremely high electrical conductivity, excellent mechanical flexibility and good light transmission. However, the dielectric in the current multilayer electrode structure still uses materials such as ITO, FTO and AZO, and the above defects have not been solved. Moreover, the metal layer between the two dielectric layers also has the problem of difficult to balance the conductivity (need to be thick enough and uniform enough) and light transmission (need to be thin enough).

[0004] In view of this, the present application is proposed. SUMMARY

[0005] The present application aims to provide a flexible transparent conductive film, a preparation method and application thereof, and a perovskite battery.

[0006] The present application is implemented as follows: In a first aspect, the present application provides a flexible transparent conductive film, comprising a transparent substrate layer and a multilayer electrode layer on the surface thereof; the multilayer electrode layer comprises a metal oxide layer and a metal layer, and the metal layer is located between two adjacent metal oxide layers.

[0007] The material of the metal oxide layer comprises a first metal oxide and a second metal oxide.

[0008] The first metal oxide comprises at least one of indium tin oxide, ZnO-doped In2O3, WO3-doped In2O3 and Al2O3-doped ZnO.

[0009] The second metal oxide comprises at least one of TiO2, SnO2, ZnO and Nb2O5.

[0010] Preferably, the molar ratio of the first metal oxide and the second metal oxide is 65:35 to 90:10.

[0011] The material of the metal layer includes Ag and a doped metal, the doped metal including at least one of Bi, Pd, Cu, Nd, In, Sn and Sb.

[0012] In an optional embodiment, the material of the metal oxide layer includes, in mole percent, a first metal oxide: 65-75 mol%, a second metal oxide of TiO2 or SnO2: 10-15 mol%, and a second metal oxide of ZnO or Nb2O5: 15-22 mol%.

[0013] Preferably, the material of the metal oxide layer includes any one of the following combinations: 1) includes, in mole percent, ZnO-doped In2O3: 65-75 mol%, TiO2: 10-15 mol%, and Nb2O5: 18-22 mol%.

[0014] 2) includes, in mole percent, WO3-doped In2O3: 65-75 mol%, SnO2: 10-15 mol%, and ZnO: 18-22 mol%.

[0015] 3) includes, in mole percent, Al2O3-doped ZnO: 65-75 mol%, TiO2: 10-15 mol%, and Nb2O5: 18-22 mol%.

[0016] In an optional embodiment, in the ZnO-doped In2O3, the mass ratio of In2O3 and ZnO is 89:11-92:8.

[0017] In the WO3-doped In2O3, the mass ratio of In2O3 and WO3 is 99.2:0.8-99.8:0.2.

[0018] In the Al2O3-doped ZnO, the mass ratio of ZnO and Al2O3 is 97.5:2.5-98.5:1.5.

[0019] In the indium tin oxide, the mass ratio of In2O3 and SnO2 is 89:11-92:8.

[0020] In an optional embodiment, in the metal layer, the mass ratio of Ag and the doped metal is 95:5-99.7:0.3.

[0021] Preferably, in the metal layer, the doped metal is Bi and / or Pd.

[0022] Preferably, in the metal layer, the mass ratio of Ag, Pd and Bi is 96:0.2:3.8-97:0.8:3.2.

[0023] In an optional embodiment, the thickness of the metal layer is 1-15 nm; and / or, the thickness of each metal oxide layer is 15-50 nm.

[0024] In an optional embodiment, the material of the transparent substrate layer comprises at least one of polyethylene terephthalate, polyimide, polyethylene naphthalate, polytetrafluoroethylene, ultra-thin glass or aluminum nitride transparent ceramic.

[0025] In a second aspect, the present application provides a method for preparing the flexible transparent conductive film as described in the foregoing embodiments, comprising depositing the multilayer electrode layer on one side of the transparent substrate layer.

[0026] Preferably, the deposition method of the multilayer electrode layer comprises at least one of electron beam vacuum deposition, magnetron sputtering or ion plating.

[0027] Preferably, the deposition of the metal layer comprises using a mixed atmosphere of argon and nitrogen as the deposition atmosphere, and the volume ratio of argon to nitrogen is 95:5-97:3.

[0028] The metal layer is deposited by direct current magnetron sputtering, and the deposition parameters include: film forming power is 180-220 W, sputtering pressure is 0.3-0.4 Pa, the flow rate of argon in the deposition atmosphere is 120-140 sccm, and the flow rate of nitrogen is 4-5 sccm.

[0029] In an optional embodiment, the metal oxide layer is deposited by direct current magnetron sputtering, and the deposition parameters include: film forming power is 420-480 W, sputtering pressure is 0.4-0.6 Pa, and sputtering temperature is 70-140℃; the deposition atmosphere comprises oxygen and inert gas, the flow rate of inert gas is 180-200 sccm, and the flow rate of oxygen accounts for 0.15-6% of the total gas flow.

[0030] The inert gas comprises at least one of Ar, He, Ne, Ar, Kr, Xe and Rn.

[0031] In a third aspect, the present application provides a perovskite battery comprising the flexible transparent conductive film as described in the foregoing embodiments.

[0032] In a fourth aspect, the present application provides the use of the flexible transparent conductive film as described in the foregoing embodiments in a touch panel, a flexible thin film photovoltaic and a wearable display device.

[0033] The present application has the following beneficial effects: The application provides a flexible transparent conductive film and a preparation method and application thereof and a perovskite battery, through adoption of a structure of a multilayer electrode layer, and the material of the metal oxide layer in the multilayer electrode layer comprises oxides of at least three metals in Ti, Nb, Zn, Sn, In, W and Al, through the above-mentioned multi-metal doping, the metal oxide layer can be endowed with good conductivity and high light transmittance, meanwhile, the defect of high brittleness of the metal oxide layer is solved, the flexibility of the metal oxide layer is improved, and the use stability is ensured. In addition, through doping of metals such as Bi, Pd, Cu, Nd, In, Sn and Sb in Ag of the metal layer, the three-dimensional growth trend of Ag can be inhibited, so that the metal layer can realize good conductivity with a thinner thickness, and the problem that the conductivity and light transmittance of the metal layer cannot be considered together is solved. BRIEF DESCRIPTION OF DRAWINGS

[0034] In order to more clearly illustrate the technical solutions of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some of the embodiments of the application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0035] Figure 1 Structure schematic diagram of the flexible transparent conductive film provided for the embodiment 1 of the application; Figure 2 Atomic force microscope (AFM) diagram of the metal layer of the flexible transparent conductive film provided for the embodiment 2 of the application; Figure 3 Atomic force microscope (AFM) diagram of the metal layer of the flexible transparent conductive film provided for the comparative example 1 of the application; Figure 4 Absorption spectrum diagram of the metal layer of the flexible transparent conductive film provided for the test example 6 of the application; Figure 5 Absorption spectrum diagram of the metal layer of the IWO / Ag / IWO transparent conductive film provided for the test example 6 of the application.

[0036] Figure legend: 100-flexible transparent conductive film; 110-transparent substrate layer; 120-multilayer electrode layer; 121-first metal oxide layer; 122-second metal oxide layer; 123-metal layer. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solutions and advantages of the embodiments of the application more clear, the technical solutions in the embodiments of the application will be clearly and completely described below. If the specific conditions are not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturers are adopted. If the reagents or instruments used are not specified by the manufacturers, they are all conventional products that can be purchased on the market.

[0038] The features and properties of the present application are further described in detail below in conjunction with the embodiments.

[0039] In a first aspect, the present application provides a flexible transparent conductive film, comprising a transparent substrate layer and a multilayer electrode layer on the surface thereof; the multilayer electrode layer comprises metal oxide layers and metal layers, and the metal layers are located between two adjacent metal oxide layers.

[0040] The common structure of the multilayer electrode layer is formed by two metal oxide layers and a metal layer between them to form a sandwich structure, i.e. a dielectric / metal / dielectric (DMD) multilayer structure, therefore, the number of metal oxide layers of the multilayer electrode layer provided by the present application is also two. In other embodiments, as long as the performance of the flexible transparent conductive film can be ensured, the number of metal oxide layers and metal layers can also be adjusted as needed.

[0041] The material of the metal oxide layer includes at least three of Ti oxide, Nb oxide, Zn oxide, Sn oxide, In oxide, W oxide and Al oxide.

[0042] The material of the metal layer includes Ag and a doped metal, and the doped metal includes at least one of Bi, Pd, Cu, Nd, In, Sn and Sb.

[0043] By adopting the structure of the multilayer electrode layer, and the material of the metal oxide layer in the multilayer electrode layer including oxides of at least three metals of Ti, Nb, Zn, Sn, In, W and Al, and by the above-mentioned multi-metal doping, the metal oxide layer can be endowed with good conductivity and high light transmittance, while solving the defect of high brittleness of the metal oxide layer, the flexibility of the metal oxide layer is improved, and the use stability is ensured. In addition, by doping metals such as Bi, Pd, Cu, Nd, In, Sn and Sb in Ag of the metal layer, the three-dimensional growth trend of Ag can be inhibited, so that the metal layer can achieve good conductivity performance with a thinner thickness, and the problem that the conductivity and light transmittance of the metal layer cannot be considered together is solved.

[0044] The material of the metal layer provided by the present application may, for example, be any one of Ag-Pd, Ag-Cu, Ag-Bi, Ag-Pd-Bi, Ag-Pd-Cu, Ag-Nd-Cu, Ag-In-Sn and Ag-Sn-Sb.

[0045] Preferably, the mass ratio of Ag and the doped metal in the metal layer is 95:5~99.7:0.3. That is, the mass percentage of Ag in the metal layer may, for example, be any one of 95wt%, 96wt%, 97wt%, 98wt%, 99wt% and 99.7wt%, or a range value between any two of them, and the balance is the doped metal.

[0046] The structure of the metal layer is closely related to the performance of the flexible transparent conductive film. Only when the thickness of the metal layer is thick enough, the metal layer can reach a penetration state to establish sufficient electrical paths, i.e., to ensure that the flexible transparent conductive film has good conductivity. Meanwhile, it is also necessary to ensure that the thickness of the metal layer is thin enough to obtain a high optical transmittance.

[0047] The inventors have found that the growth of the metal in the metal layer on the surface of the metal oxide layer includes several stages, such as nucleation, coalescence and thickness growth. The material composition and surface performance of the metal oxide layer, as well as the material of the metal layer and various parameters in the deposition process, will affect the quality of the metal layer.

[0048] For example, in the nucleation process, the growth of the metal in the metal layer depends on whether the force between adjacent metal atoms or the force between the metal atoms and the atoms of the metal oxide layer dominates. The growth mode of the metal switches between the Volmer-Weber mode and the Frank-van der Merwe mode, and the surface morphology tends to be a continuous and flat film structure from isolated three-dimensional atomic islands. When the growth of the metal is dominated by the Volmer-Weber mode, the island-like structure of the metal formed will induce the formation of localized surface plasmon resonance, which in turn will cause the absorption of light of a specific wavelength, resulting in a decrease in the light transmittance of the electrode. Therefore, in order to obtain a metal layer with a flat surface topography and good photoelectric performance, it is necessary to suppress the Volmer-Weber growth mode.

[0049] From the material of the metal layer, the present application can improve the wettability and corrosion resistance of Ag on the surface of the metal oxide layer by doping a small amount of Bi and / or Pd in Ag, which is beneficial to obtain an Ag thin film by reducing the thickness and grain size of the Ag layer. At the same time, the doping of bismuth can also inhibit the three-dimensional growth of Ag, so that the metal layer provided by the present application can achieve better conductivity with a thinner thickness, and the comprehensive performance of the flexible transparent conductive film is significantly improved.

[0050] Therefore, preferably, the doping metal in the metal layer is Bi and / or Pd; the material of the metal layer may, for example, be Bi-doped metal Ag (Ag-Bi), Pd-doped metal Ag (Ag-Pd) or Bi and Pd co-doped metal Ag (Ag-Pd-Bi).

[0051] Further preferably, the material of the metal layer is Bi-doped metal Ag (Ag-Bi) or Bi and Pd co-doped metal Ag (Ag-Pd-Bi); more preferably, it is Bi and Pd co-doped metal Ag (Ag-Pd-Bi).

[0052] In an optional embodiment, the mass ratio of Ag, Pd and Bi in the metal layer is 95:0.2:3.8~99.7:0.8:3.2.

[0053] From the material composition and surface performance of the metal oxide layer, the metal oxide layer is prepared by using at least three metal oxides among Ti, Nb, Zn, Sn, In, W and Al in the application, which can improve the brittleness of the traditional metal oxide (ITO, FTO and AZO), is conducive to the preparation of flexible transparent conductive film, and the surface performance of the metal oxide layer obtained by doping a plurality of metal oxides is excellent, which is suitable for the growth of metal on the surface, so as to ensure the comprehensive performance of the flexible transparent conductive film.

[0054] The material selection of the metal oxide layer provided by the embodiment of the application is as follows: The material of the metal oxide layer includes a first metal oxide and a second metal oxide.

[0055] The first metal oxide is a double-metal doped oxide, and includes at least one of indium tin oxide (ITO), ZnO doped In2O3 (IZO), WO3 doped In2O3 (IWO) and Al2O3 doped ZnO (AZO).

[0056] The first metal oxide is preferably doped first and then mixed with the second metal oxide, and in other embodiments, each metal oxide in the first metal oxide can also be mixed with the second metal oxide.

[0057] The second metal oxide is a single-metal oxide, and includes at least one of TiO2, SnO2, ZnO and Nb2O5.

[0058] By doping at least one second metal oxide on the basis of the first metal oxide, the performance of the first metal oxide can be significantly improved. For example, when TiO2 is doped, the refractive index of the metal oxide layer can be improved, so that the light transmittance of the flexible transparent conductive film can be improved; when SnO2 and Nb2O5 are doped, the metal oxide layer can inhibit the occurrence of cracks and improve the bending resistance of the flexible transparent conductive film; when ZnO is doped, the conductivity of the metal oxide layer is enhanced.

[0059] Preferably, the molar ratio of the first metal oxide and the second metal oxide is 65:35~90:10.

[0060] That is, the molar percentage of the first metal oxide in the metal oxide layer may, for example, be any one of 65mol%, 70mol%, 75mol%, 80mol%, 85mol% and 90mol% or a range value between any two of them, and the balance is the second metal oxide.

[0061] Preferably, the material of the metal oxide layer comprises, in mole percent, a first metal oxide: 65-75 mol%, TiO2or SnO2: 10-15 mol%, and ZnO or Nb2O5: 15-22 mol%. That is, the material of the metal oxide layer comprises one first metal oxide and two second metal oxides.

[0062] When the content of TiO2is less than 10 mol%, the barrier property of the metal oxide layer to environmental substances such as moisture decreases, and the resistance value and the transmittance deteriorate over time. In addition, since Ti also has the effect of increasing the refractive index of the metal oxide layer, if the content of Ti is low, the refractive index of the metal oxide layer cannot be increased, and when the film thickness of the metal layer is large, the change in the color tone of the transmitted light is not completely suppressed, and the color reproducibility deteriorates. When the content of TiO2is more than 15 mol%, the content of the remaining metal oxides is small, and the performance of the metal oxide layer is poor.

[0063] When the content of SnO2is less than 10 mol%, the metal oxide layer is amorphous, increasing the probability of cracks occurring when bent, and reducing the bending resistance. When the content of SnO2is more than 15 mol%, the content of the remaining metal oxides is small, and the performance of the metal oxide layer is poor.

[0064] When the content of ZnO is less than 15 mol%, the conductivity of the metal oxide layer decreases, and the surface resistance stability of the metal oxide layer decreases. When the content of ZnO is more than 22 mol%, the content of the remaining metal oxides is small, and the performance of the metal oxide layer is poor.

[0065] When the content of Nb2O5is less than 15 mol%, the metal oxide layer is amorphous, increasing the probability of cracks occurring when bent, and reducing the bending resistance. When the content of Nb2O5is more than 22 mol%, the content of the remaining metal oxides is small, and the performance of the metal oxide layer is poor.

[0066] Preferably, the material of the metal oxide layer comprises any one of the following combinations: 1) ZnO-doped In2O3(i.e. IZO): 65-75 mol%, TiO2: 10-15 mol%, and Nb2O5: 18-22 mol%, in mole percent; more preferably, IZO: 68 mol%, TiO2: 12 mol%, and Nb2O5: 20 mol%.

[0067] 2) WO3-doped In2O3(i.e. IWO): 65-75 mol%, SnO2: 10-15 mol%, and ZnO: 18-22 mol%, in mole percent.

[0068] 3) 65-75 mol% of Al2O3-doped ZnO (i.e. AZO), 10-15 mol% of TiO2, and 18-22 mol% of Nb2O5, in terms of mole percentage.

[0069] By selecting any one of the above three combinations, the metal oxide layer has both excellent electrical conductivity and light transmittance, and is conducive to the growth of a uniform and thin metal layer, thereby improving the comprehensive performance of the flexible transparent conductive film.

[0070] In an optional embodiment, in ZnO-doped In2O3 (IZO), the mass ratio of In2O3 to ZnO is 89:11-92:8, and is preferably 90:10.

[0071] In WO3-doped In2O3 (IWO), the mass ratio of In2O3 to WO3 is 99.2:0.8-99.8:0.2, and is preferably 99.5:0.5.

[0072] In Al2O3-doped ZnO (AZO), the mass ratio of ZnO to Al2O3 is 97.5:2.5-98.5:1.5, and is preferably 98:2.

[0073] In indium tin oxide (ITO), the mass ratio of In2O3 to SnO2 is 89:11-92:8, and is preferably 90:10.

[0074] By controlling the content of each metal oxide in ITO, IWO, IZO, and AZO in the first metal oxide within the above range, the electrical conductivity and light transmittance of the metal oxide layer can be ensured to be both excellent.

[0075] In an optional embodiment, the thickness of the metal layer is 1-15 nm, preferably 3-12 nm, and more preferably 4-10 nm. When the thickness of the metal layer is less than 1 nm, the control precision of the metal layer preparation process is required to be high, the preparation is difficult, and the electrical conductivity is poor. When the thickness of the metal layer is greater than 15 nm, the transmittance of the metal layer is poor.

[0076] In an optional embodiment, the thickness of each metal oxide layer is 15-50 nm, preferably 20-40 nm, and more preferably 30-40 nm. When the thickness of each metal oxide layer is less than 15 nm or greater than 50 nm, the light interference effect of the metal oxide layer for converting the reflected light in the metal thin film into transmitted light can deviate from the optimal condition, resulting in poor light transmittance.

[0077] In an optional embodiment, the material of the transparent substrate layer comprises at least one of polyethylene terephthalate (PET), polyimide (PI), polyethylene naphthalate (PEN), polytetrafluoroethylene (PTFE), ultra-thin glass (UTG) or aluminum nitride transparent ceramic (ALON). Preferably, the material of the transparent substrate layer is polyethylene naphthalate (PEN).

[0078] In a second aspect, the present application provides a method for preparing the flexible transparent conductive film as described in the foregoing embodiments, comprising depositing a multilayer electrode layer on one side of the transparent substrate layer.

[0079] The binding ability between Ag and the existing metal oxide materials ITO, FTO and AZO is poor, so a thin Cu layer (about 0.1 nm thick) is usually deposited before depositing the Ag layer to improve the wettability of Ag to AZO. However, the addition of the Cu layer not only increases the number of sputtering target sites, increasing the cost of equipment and production, but also requires a very high film forming process to control the thickness of the Cu layer to 0.1 nm, which is difficult to control, resulting in difficulty in controlling the stability of the flexible transparent conductive film in terms of sheet resistance and transmittance.

[0080] The flexible transparent conductive film provided by the present application does not need to additionally set a copper layer or other metal seed layer, does not increase the production cost, and has a suitable thickness of the metal layer, so that the deposition operation is simple and easy to control, which is conducive to ensuring the surface sheet resistance stability and transmittance stability of the flexible transparent conductive film, and in combination with the material selection of the present application, a flexible transparent conductive film with low surface sheet resistance and high transmittance can be obtained.

[0081] Preferably, the deposition method of the multilayer electrode layer comprises at least one of electron beam vacuum deposition, magnetron sputtering or ion plating, preferably magnetron sputtering.

[0082] Preferably, the deposition process of the metal layer comprises using a mixed atmosphere of argon and nitrogen as the deposition atmosphere, and the volume ratio of argon to nitrogen is 95:5 to 97:3. The incorporation of a small amount of nitrogen during the deposition of the metal layer not only further improves the wettability of Ag to the surface of the metal oxide layer, but also better inhibits the Volmer-Weber growth mode of the metal during the film forming process, thereby ensuring that the metal layer has good light transmission ability, conductivity and bending resistance while reducing the thickness of the metal layer.

[0083] The metal layer is deposited by direct current magnetron sputtering, and the deposition parameters include: a film forming power of 180-220 W, a sputtering pressure of 0.3-0.4 Pa, an argon flow rate of 120-140 sccm, and a nitrogen flow rate of 4-5 sccm. By controlling the preparation parameters of the metal layer within the above range, a metal layer with uniform morphology, thin thickness, and good bonding capacity with the metal oxide layer can be obtained.

[0084] Since the metal layer is a material composed of Ag and a doped metal, in the process of preparing the metal layer, the Ag and the doped metal are preferably mixed in proportion to prepare an alloy target material, and then the alloy target material is used for direct current magnetron sputtering deposition; in other embodiments, a pure silver target material and a pure metal target material of the doped metal can also be used for magnetron sputtering deposition in proportion.

[0085] In an optional embodiment, the metal oxide layer is deposited by direct current magnetron sputtering, and the deposition parameters include: a film forming power of 420-480 W, a sputtering pressure of 0.4-0.6 Pa, and a sputtering temperature of 70-140℃; the deposition atmosphere includes oxygen and an inert gas, the flow rate of the inert gas is 180-200 sccm, and the oxygen flow rate accounts for 0.15-6% of the total gas flow rate.

[0086] The inert gas includes at least one of Ar, He, Ne, Ar, Kr, Xe, and Rn, and is preferably argon (Ar).

[0087] By controlling the preparation parameters of the metal oxide layer within the above range, the transmittance and conductivity of the metal oxide can be adjusted to ensure the conductivity and light effect of the metal oxide layer, so that a flexible transparent conductive film with good comprehensive performance is obtained.

[0088] In a third aspect, the present application provides a perovskite battery including the flexible transparent conductive film according to the foregoing embodiments.

[0089] In a fourth aspect, the present application provides an application of the flexible transparent conductive film according to the foregoing embodiments in a touch panel, a flexible thin film photovoltaic, and a wearable display device.

[0090] The meanings and detection methods of the performance parameters of the flexible transparent conductive film / transparent conductive film provided in the following examples and comparative examples are as follows (the "sample" in the detection method refers to the flexible transparent conductive film / transparent conductive film provided in the corresponding example or comparative example): Tone evaluation Color measurement, color difference analysis and color quality evaluation were performed using a spectrophotometer. The evaluation results were shown using a* and b* values in the L*a*b color system. When the values of a* and b* were in the range of -1 to 1, it was considered that the color tone change was difficult to recognize by the human eye, which was a preferred case. In order to ensure that the sample still had stable color reproducibility after long-term use, the closer the a* and b* values were to zero, the more preferred they were.

[0091] Transmittance detection The average transmittance of the sample in the range of 400 nm to 800 nm was measured using a spectrophotometer. The principle was to decompose the light source into monochromatic light through a spectrometer (grating or prism), and measure the transmitted light intensity of the sample by wavelength. The closer the transmittance percentage value was to 100%, the better it was.

[0092] Sheet resistance stability detection A 4-probe sheet resistance meter was used for measurement. Ten different points on the sample were selected for continuous measurement of each point for 15 seconds. The average value of the surface sheet resistance (R ave ) displayed by all measurement points was calculated. Then, the change rate of the surface sheet resistance was calculated according to (R max -R min ) / R ave *100%. The larger the value, the worse the conductivity of the film layer, and the smaller the value, the better the conductivity of the film layer.

[0093] Environmental resistance test The sample was placed in a constant temperature oven at 85°C and 85% RH for 200 hours. The transmittance of the sample before and after the holding was detected, and the transmittance drop was calculated according to "transmittance before holding-transmittance after holding". The surface sheet resistance of the sample before holding (R1) and after holding (R2) was detected, and the surface sheet resistance rise rate before and after holding was calculated according to "(R1-R2) / R2*100%". When the transmittance drop of the sample was less than 1% and the surface sheet resistance rise rate was less than 10%, the environmental resistance of the sample was evaluated as "A", and the rest was evaluated as "B". When the environmental resistance of the sample was evaluated as "A", the sample could ensure long-term stable driving performance in its use environment when applied to a touch panel.

[0094] Bending test The sample is wound on a 8mm diameter cylinder, and the surface resistance of the sample before and after bending is measured by a 4-probe surface resistance meter. The surface resistance of the sample before bending is taken as R1, and the surface resistance of the sample after bending is taken as R3. The surface resistance change rate (rise rate) of the sample before and after bending is calculated according to "(R3-R1) / R1*100%". The smaller the surface resistance change rate, the better the performance of the sample. When the surface resistance change rate of the sample is less than 1.1%, it is evaluated as "A", and the rest is evaluated as "B". The sample evaluated as "A" in the bending test can withstand the influence of repeated heating, extrusion and other operations in the manufacturing process, and can also ensure the performance stability of the final product during use.

[0095] Example 1 Please refer to Figure 1 The embodiment provides a flexible transparent conductive film 100, which comprises a transparent substrate layer 110 and a multilayer electrode layer 120 on the surface thereof.

[0096] The material of the transparent substrate layer 110 is polyethylene naphthalate (PEN), and the thickness is 80 μm.

[0097] The multilayer electrode layer 120 is a sandwich structure composed of two metal oxide layers and a metal layer 123 between the two metal oxide layers, wherein the first metal oxide layer 121 is closely connected with the transparent substrate layer.

[0098] The materials of the two metal oxide layers are the same, and the material of each metal oxide layer comprises, in terms of mole percentage, 68 mol% of WO3-doped In2O3 (IWO), 12 mol% of TiO2 and 20 mol% of Nb2O5.

[0099] The material of the metal layer comprises, in terms of mass percentage, 96.5 wt% of Ag, 0.5 wt% of Pd and 3 wt% of Bi.

[0100] The embodiment also provides a preparation method of the above flexible transparent conductive film 100, comprising the following steps. S01, polyethylene naphthalate (PEN) material with a thickness of 80 μm is used as the transparent substrate layer 110, and a direct current magnetron sputtering is used to deposit the first metal oxide layer 121 on one side of the transparent substrate layer 110. The deposition parameters of the first metal oxide layer 121 include that the deposition atmosphere is argon and a small amount of oxygen, the argon flow rate is 190 sccm, the oxygen flow rate is 0.3 sccm, the film forming power is 450 W, the sputtering pressure is 0.5 Pa, and the sputtering temperature is 70°C. The thickness of the obtained first metal oxide layer 121 is 35 nm.

[0101] S02. A metal layer 123 was deposited on the surface of the first metal oxide layer 121 by DC magnetron sputtering. The deposition parameters of the metal layer 123 included: a deposition atmosphere of a mixture of 96.5 wt% argon and 3.5 wt% nitrogen, an argon flow rate of 130 sccm, a nitrogen flow rate of 4.55 sccm, a film forming power of 200 W, and a sputtering pressure of 0.36 Pa. The thickness of the deposited metal layer 123 was 8 nm.

[0102] S03. Depositing a second metal oxide layer 122 on the surface of the metal layer 123 by DC magnetron sputtering. The deposition parameters of the second metal oxide layer 122 include: a deposition atmosphere of argon and a small amount of oxygen, an argon flow rate of 190 sccm, an oxygen flow rate of 0.1 sccm, a film forming power of 450 W, a sputtering pressure of 0.5 Pa, and a sputtering temperature of 70° C. The thickness of the deposited second metal oxide layer 122 is 36 nm.

[0103] Example 2 This embodiment provides a flexible transparent conductive film and a preparation method thereof, which is different from the embodiment 1 only in that the sputtering temperature of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 are both 100°C.

[0104] The metal layer 123 deposited in this embodiment was placed under an atomic force microscope (AFM) for observation, and the following was obtained: Figure 2 The results shown in the figure show that the surface root mean square roughness (Sq) is analyzed based on its surface morphology, and the Sq is 6.41. Its particle size is small, indicating that the three-dimensional growth mode of Ag is suppressed, and high transmittance and surface resistance can be achieved at a lower thickness.

[0105] Example 3 This embodiment provides a flexible transparent conductive film and a preparation method thereof. The only difference from the first embodiment is that the sputtering temperature of the first metal oxide layer 121 and the second metal oxide layer 122 are both 120° C.

[0106] Example 4 This embodiment provides a flexible transparent conductive film and a preparation method thereof. The only difference from the first embodiment is that the sputtering temperature of the first metal oxide layer 121 and the second metal oxide layer 122 are both 140° C.

[0107] Example 5 This embodiment provides a flexible transparent conductive film and a preparation method thereof. The only difference from Example 1 is that the material of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 is a mixture of indium tin oxide (ITO), niobium oxide (Nb2O5) and titanium oxide (TiO2).

[0108] In2O3:SnO2=90:10, and ITO:Nb2O5:TiO2=65:20:15.

[0109] In2O3:SnO2=90:10, and ITO:Nb2O5:TiO2=65:20:15.

[0110] Example 6 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 5 is that the sputtering temperature of the first metal oxide layer 121 in the step S01 and the second metal oxide layer 122 in the step S02 is 100°C.

[0111] Example 7 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 5 is that the sputtering temperature of the first metal oxide layer 121 in the step S01 and the second metal oxide layer 122 in the step S02 is 120°C.

[0112] Example 8 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 5 is that the sputtering temperature of the first metal oxide layer 121 in the step S01 and the second metal oxide layer 122 in the step S02 is 140°C.

[0113] Example 9 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 5 is that the molar ratio of ITO, Nb2O5 and TiO2 is 90:6:4.

[0114] In2O3:SnO2=90:10, and ITO:Nb2O5:TiO2=65:20:15.

[0115] Example 10 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 1 is that the material of the first metal oxide layer 121 in the step S01 and the second metal oxide layer 122 in the step S02 is a mixture of ZnO doped In2O3 (IZO), Nb2O5 and TiO2.

[0116] IZO, Nb2O5and TiO2are 65:20:15.

[0117] That is, the molar amount of IZO is 65mol, the molar amount of Nb2O5is 20mol, and the molar amount of TiO2is 15mol.

[0118] Example 11 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 10 is that the sputtering temperature of the first metal oxide layer 121 in the step S01 and the sputtering temperature of the second metal oxide layer 122 in the step S02 are both 100℃.

[0119] Example 12 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 10 is that the sputtering temperature of the first metal oxide layer 121 in the step S01 and the sputtering temperature of the second metal oxide layer 122 in the step S02 are both 120℃.

[0120] Example 13 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 10 is that the sputtering temperature of the first metal oxide layer 121 in the step S01 and the sputtering temperature of the second metal oxide layer 122 in the step S02 are both 140℃.

[0121] Example 14 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 10 is that the molar ratio of IZO, Nb2O5and TiO2is 90:6:4.

[0122] That is, the molar amount of IZO is 90mol, the molar amount of Nb2O5is 6mol, and the molar amount of TiO2is 4mol.

[0123] Comparative Example 1 The comparative example provides a transparent conductive film, and the difference from the embodiment 2 is that the metal oxide layer is ITO material, and the Sn:In2O3in the ITO is 90:10; and the metal layer is pure silver material.

[0124] The comparative example also provides a preparation method of the above transparent conductive film, and the difference from the embodiment 2 is that the deposition atmosphere in the step S02 is 100wt% argon.

[0125] The metal layer 123 obtained by deposition in the comparative example is observed under an atomic force microscope (AFM), and the obtained image is as shown inFigure 3 According to the results, the surface root mean square roughness (Sq) of the surface was analyzed according to the surface topography, and the Sq was 16.7, the particle size was large, and the Ag layer tended to grow in the thickness direction.

[0126] Comparative Example 2 The present comparative example provides a transparent conductive film, which is different from the example 3 only in that the metal oxide layer is an ITO material, the Sn:In2O3 in the ITO is 90:10, and the metal layer is a pure silver material.

[0127] The present comparative example also provides a preparation method of the above transparent conductive film, which is different from the example 3 only in that the deposition atmosphere in the S02 step is 100wt% argon.

[0128] Comparative Example 3 The present comparative example provides a transparent conductive film, which is different from the example 4 only in that the metal oxide layer is an ITO material, the Sn:In2O3 in the ITO is 90:10, and the metal layer is a pure silver material.

[0129] The present comparative example also provides a preparation method of the above transparent conductive film, which is different from the example 4 only in that the deposition atmosphere in the S02 step is 100wt% argon.

[0130] Test Example 1 The flexible transparent conductive films provided by the examples 1-9 and the transparent conductive films provided by the comparative examples 1-3 were subjected to color tone evaluation, transmittance detection, sheet resistance stability detection, environmental resistance detection and bending resistance detection, and the results are shown in Table 1.

[0131] Table 1 Performance of flexible transparent conductive film and transparent conductive film

[0132] Referring to the data in Table 1, the transparent conductive films prepared by the comparative examples 1-3 adopt a multilayer electrode layer structure of ITO / Ag / ITO, the values of the parameters a* and b* are large, the color reproducibility is poor, the transmittance is low, the surface sheet resistance is large, and the environmental resistance and bending resistance evaluations are poor, indicating that the traditional multilayer electrode layer structure of ITO / Ag / ITO is difficult to meet the high performance requirements of the transparent conductive film. The values of a* and b* of the examples of the present application are closer to 0 than those of the comparative examples, the color reproducibility of the flexible transparent conductive film is excellent, the transmittance is high, the surface sheet resistance is low, the environmental resistance and bending resistance are excellent, and the performance of the flexible transparent conductive film is better and more stable.

[0133] In addition, as can be seen from Examples 1-4, Examples 5-8, Examples 10-13 and Comparative Examples 1-3, the performance of the flexible transparent conductive film varies significantly with the sputtering temperature of the metal oxide layer, the transmittance increases with the sputtering temperature, and the surface sheet resistance decreases with the sputtering temperature.

[0134] As can be seen from Example 9 and Example 14, the performance of the flexible transparent conductive film obtained by replacing ITO with IZO is comparable, with good light transmittance and low surface sheet resistance, good environmental resistance, and excellent application value. Example 15 This example provides a flexible transparent conductive film and a preparation method thereof, which differs from Example 4 only in that the thickness of the metal layer 123 is 6 nm.

[0135] Example 16 This example provides a flexible transparent conductive film and a preparation method thereof, which differs from Example 15 only in that in the S02 step, the deposition atmosphere for depositing the metal layer is 100 wt% argon.

[0136] Example 17 This example provides a flexible transparent conductive film and a preparation method thereof, which differs from Example 4 only in that the thickness of the metal layer 123 is 7 nm.

[0137] Example 18 This example provides a flexible transparent conductive film and a preparation method thereof, which differs from Example 4 only in that the thickness of the metal layer 123 is 9 nm.

[0138] Comparative Example 4 This comparative example provides a transparent conductive film, which has the same structure as Comparative Example 1, and the difference between the preparation method of this comparative example and that of Comparative Example 1 is only that the thickness of the metal layer 123 is 6 nm.

[0139] Comparative Example 5 This comparative example provides a transparent conductive film, which has the same structure as Comparative Example 1, and the difference between the preparation method of this comparative example and that of Comparative Example 1 is only that the thickness of the metal layer 123 is 7 nm.

[0140] Comparative Example 6 This comparative example provides a transparent conductive film, which has the same structure as Comparative Example 1, and the difference between the preparation method of this comparative example and that of Comparative Example 1 is only that the thickness of the metal layer 123 is 9 nm.

[0141] Test Example 2 The flexible transparent conductive films provided by Examples 15-18 and the transparent conductive films provided by Comparative Examples 4-6 were subjected to color tone evaluation, transmittance detection, sheet resistance stability detection, environmental resistance detection, and bending resistance detection, and the results are shown in Table 2.

[0142] Table 2 Performance of flexible transparent conductive film and transparent conductive film

[0143] Referring to the data in Table 2, the color reproducibility of Comparative Example 4 is better, the transmittance is better, but the surface sheet resistance is larger, and the environmental resistance is poorer; the color reproducibility of Comparative Example 5 is better, the transmittance is poorer, and the surface sheet resistance is larger, and the environmental resistance is poorer; although the surface sheet resistance of Comparative Example 6 is reduced, the color reproducibility is poorer, the transmittance is poorer, and the environmental resistance is poorer.

[0144] It is shown that the transparent conductive film prepared by the conventional ITO / Ag / ITO multilayer electrode layer structure cannot simultaneously have high transmittance (88.6% of Comparative Example 4) and low surface sheet resistance (8.3 Ω / □ of Comparative Example 6), while the embodiment 17 of the present application can simultaneously have high transmittance (90.6%) and low surface sheet resistance (9.7 Ω / □), and the comprehensive performance of the flexible transparent conductive film is better.

[0145] Embodiment 19 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the only difference from the embodiment 4 is that the thickness of the first metal oxide layer 121 is 40 nm.

[0146] Embodiment 20 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the only difference from the embodiment 4 is that the thickness of the first metal oxide layer 121 is 30 nm.

[0147] Embodiment 21 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the only difference from the embodiment 4 is that the thickness of the first metal oxide layer 121 is 20 nm.

[0148] Embodiment 22 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the only difference from the embodiment 4 is that the thickness of the first metal oxide layer 121 is 15 nm.

[0149] Test Example 3 The flexible transparent conductive films provided by the embodiments 19-22 are subjected to color tone evaluation, transmittance detection, sheet resistance stability detection, environmental resistance detection, and bending resistance detection, and the results are shown in Table 3.

[0150] Table 3 Performance of flexible transparent conductive film

[0151] As shown in Table 3, the surface resistivity and transmittance of the flexible transparent conductive film decrease slightly with increasing thickness of the first metal oxide layer 121. Specifically, when the thickness of the first metal oxide layer 121 is between 30 and 40 nm, the a* and b* values ​​of the hue evaluation are relatively low, indicating excellent color reproducibility and stable transmittance.

[0152] Example 23 This embodiment provides a flexible transparent conductive film and a preparation method thereof, which is different from the embodiment 2 only in that the prepared flexible transparent conductive film is annealed at an annealing temperature of 100° C. for 30 minutes.

[0153] Example 24 This embodiment provides a flexible transparent conductive film and a preparation method thereof, which is different from Example 2 only in that the prepared flexible transparent conductive film is annealed at a temperature of 150° C. for 30 minutes.

[0154] Example 25 This embodiment provides a flexible transparent conductive film and a preparation method thereof, which is different from Example 2 only in that the prepared flexible transparent conductive film is annealed at a temperature of 200° C. for 30 minutes.

[0155] Example 26 This embodiment provides a flexible transparent conductive film and a preparation method thereof, which is different from the embodiment 3 only in that the prepared flexible transparent conductive film is annealed at an annealing temperature of 100° C. and an annealing time of 30 min.

[0156] Example 27 This embodiment provides a flexible transparent conductive film and a preparation method thereof, which is different from the embodiment 3 only in that the prepared flexible transparent conductive film is annealed at a temperature of 150° C. for 30 minutes.

[0157] Example 28 This embodiment provides a flexible transparent conductive film and a preparation method thereof, which is different from the embodiment 3 only in that the prepared flexible transparent conductive film is annealed at a temperature of 200° C. for 30 minutes.

[0158] Example 29 This embodiment provides a flexible transparent conductive film and a preparation method thereof, which is different from the embodiment 4 only in that the prepared flexible transparent conductive film is annealed at an annealing temperature of 100° C. and an annealing time of 30 min.

[0159] Example 30 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 4 is that the prepared flexible transparent conductive film is subjected to annealing treatment, the annealing temperature of the step is 150 DEG C, and the annealing time is 30 min.

[0160] Embodiment 31 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 4 is that the prepared flexible transparent conductive film is subjected to annealing treatment, the annealing temperature of the step is 200 DEG C, and the annealing time is 30 min.

[0161] Test example 4 The flexible transparent conductive films provided in the embodiments 23 to 31 are subjected to tone evaluation, transmittance detection, sheet resistance stability detection, environmental resistance detection and bending resistance detection, and the results are shown in Table 4.

[0162] Table 4 Performance of the flexible transparent conductive film

[0163] According to the data in Table 4, after the annealing treatment of the flexible transparent conductive film provided in the embodiments, the performance of the flexible transparent conductive film is not reduced, but the crystallinity of the metal oxide layer is promoted, the conductivity and the transmittance of the oxide layer are improved, the surface sheet resistance of the flexible transparent conductive film is reduced with the increase of the annealing temperature of the flexible transparent conductive film, and when the sputtering temperature of the metal oxide layer is 140 DEG C and the annealing temperature is 150 DEG C to 200 DEG C (i.e. the embodiments 30 and 31), the comprehensive performance of the flexible transparent conductive film is best.

[0164] Embodiment 32 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 19 is that the material of the metal layer 123 comprises Ag: 99.5wt% and Pd: 0.5wt% according to the mass percentage.

[0165] Embodiment 33 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 20 is that the material of the metal layer 123 comprises Ag: 97wt% and Bi: 3wt% according to the mass percentage.

[0166] Embodiment 34 The embodiment provides a flexible transparent conductive film and a preparation method thereof, and the difference from the embodiment 1 is that the material of the first metal oxide layer 121 in the step S01 and the material of the second metal oxide layer 122 in the step S02 are a mixture of WO3 doped In2O3 (IWO), tin oxide (SnO2) and zinc oxide (ZnO).

[0167] The molar ratio of tungsten oxide (WO3) to indium oxide (In2O3) in the IWO is 99.2:0.8, and the molar ratio of IWO, SnO2 and ZnO is 65:15:20.

[0168] That is, the molar amount of WO3-doped In2O3 (IWO) is 65 mol, the molar amount of SnO2 is 15 mol, and the molar amount of ZnO is 20 mol.

[0169] Example 35 The present example provides a flexible transparent conductive film and a preparation method thereof, which is different from example 34 only in that the molar ratio of IWO, SnO2 and ZnO is 70:12:18.

[0170] That is, the molar amount of WO3-doped In2O3 (IWO) is 70 mol, the molar amount of SnO2 is 12 mol, and the molar amount of ZnO is 18 mol.

[0171] Example 36 The present example provides a flexible transparent conductive film and a preparation method thereof, which is different from example 34 only in that the molar ratio of IWO, SnO2 and ZnO is 75:10:15.

[0172] That is, the molar amount of WO3-doped In2O3 (IWO) is 75 mol, the molar amount of SnO2 is 10 mol, and the molar amount of ZnO is 15 mol.

[0173] Comparative Example 7 The present comparative example provides a transparent conductive film, which has a structure similar to that of example 22, and the only difference is that the material of the metal layer is pure silver.

[0174] The present comparative example also provides a preparation method of the above transparent conductive film, which is different from example 22 only in that the deposition atmosphere in the S02 step is 100wt% argon.

[0175] Test Example 5 The flexible transparent conductive film / transparent conductive film provided by examples 32-36 and comparative example 7 was subjected to color tone evaluation, transmittance detection, sheet resistance stability detection, environmental resistance detection and bending resistance detection, and the results are shown in Table 5.

[0176] Table 5 Performance of flexible transparent conductive film / transparent conductive film

[0177] Referring to the data in Table 5, the surface sheet resistance of comparative example 7 is significantly increased, and its comprehensive performance is poorer than that of the examples.

[0178] Test Example 6 A group of flexible transparent conductive films with different thickness of metal layer was prepared according to the method of Example 17, and the thickness of the metal layer was 3 nm, 5 nm, 7 nm, 9 nm and 11 nm respectively.

[0179] Meanwhile, a group of IWO / Ag / IWO transparent conductive films was prepared according to the method of Comparative Example 5, and the thickness of the metal layer of the flexible transparent conductive film in the IWO / Ag / IWO transparent conductive film was 3 nm, 5 nm, 7 nm, 9 nm and 11 nm respectively.

[0180] The above flexible transparent conductive films and IWO / Ag / IWO transparent conductive films were subjected to spectral analysis, and the results are shown in Figures Figure 4 and 5.

[0181] It can be seen from Figures Figure 5 that the conventional IWO / Ag / IWO transparent conductive film prepared composite electrode has better transmittance at 600 nm wavelength, and the transmittance drops linearly after 600 nm, resulting in a very narrow half-wave peak. Figure 4 In the present application, the flexible transparent conductive film provided by the embodiments of the present application has higher transmittance at 600 nm after the metal oxide layer and the metal layer are doped, and the transmittance slowly decreases after 600 nm, and the half-wave peak is wider.

[0182] The above is only a preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A flexible transparent conductive film, characterized in that: It comprises a transparent substrate layer and a multilayer electrode layer on the surface thereof; the multilayer electrode layer comprises a metal oxide layer and a metal layer, and the metal layer is located between two adjacent metal oxide layers; The material of the metal oxide layer includes a first metal oxide and a second metal oxide; The first metal oxide comprises at least one of indium tin oxide, ZnO doped In2O3, WO3 doped In2O3 and Al2O3 doped ZnO; The second metal oxide includes at least one of TiO2, SnO2, ZnO and Nb2O5; The molar ratio of the first metal oxide to the second metal oxide is 65:35 to 90:10; The material of the metal layer includes Ag and a doping metal, and the doping metal includes at least one of Bi, Pd, Cu, Nd, In, Sn, and Sb.

2. The flexible transparent conductive film according to claim 1, wherein: The materials of the metal oxide layer include, by mole percentage, 65-75 mol% of the first metal oxide, 10-15 mol% of TiO2 or SnO2 in the second metal oxide, and 15-22 mol% of ZnO or Nb2O5 in the second metal oxide.

3. The flexible transparent conductive film according to claim 2, wherein: The material of the metal oxide layer includes any one of the following combinations: 1) In terms of molar percentage, it includes ZnO-doped In2O3: 65-75 mol%, TiO2: 10-15 mol% and Nb2O5: 18-22 mol%; 2) In terms of molar percentage, it includes WO3 doped with In2O3: 65~75mol%, SnO2: 10~15mol% and ZnO: 18~22mol%; 3) In terms of molar percentage, it includes Al2O3 doped ZnO: 65~75mol%, TiO2: 10~15mol% and Nb2O5: 18~22mol%.

4. The flexible transparent conductive film according to claim 1, wherein: In the ZnO-doped In2O3, the mass ratio of In2O3 to ZnO is 89:11-92:8; In the WO3 doped In2O3, the mass ratio of In2O3 to WO3 is 99.2:0.8~99.8:0.2; In the Al2O3-doped ZnO, the mass ratio of ZnO to Al2O3 is 97.5:2.5~98.5:1.5; In the indium tin oxide, the mass ratio of In2O3 to SnO2 is 89:11~92:

8.

5. The flexible transparent conductive film according to claim 1, wherein: The mass ratio of Ag to doped metal in the metal layer is 95:5 to 99.7:0.

3.

6. The flexible transparent conductive film according to claim 5, characterized in that: The doping metal in the metal layer is Bi and / or Pd.

7. The flexible transparent conductive film according to claim 6, characterized in that: The metal layer is composed of Ag, Pd and Bi, and the mass ratio of Ag, Pd and Bi is 96:0.2:3.8~97:0.8:3.

2.

8. The flexible transparent conductive film according to claim 1, wherein: The thickness of the metal layer is 1-15 nm; and / or the thickness of each metal oxide layer is 15-50 nm.

9. The flexible transparent conductive film according to claim 1, wherein: The material of the transparent base layer includes at least one of polyethylene terephthalate, polyimide, polyethylene naphthalate, polytetrafluoroethylene, ultra-thin glass or aluminum nitride transparent ceramic.

10. A method for preparing a flexible transparent conductive film according to any one of claims 1 to 9, characterized in that: The method includes depositing the multi-layer electrode layer on one side of the transparent substrate layer.

11. The preparation method according to claim 10, characterized in that: The deposition method of the multi-layer electrode layer includes at least one of electron beam vacuum deposition, magnetron sputtering or ion plating.

12. The preparation method according to claim 11, characterized in that The metal oxide layer is deposited by DC magnetron sputtering, and the deposition parameters include: film forming power of 420-480W, sputtering pressure of 0.4-0.6Pa, and sputtering temperature of 70-140°C; the deposition atmosphere includes oxygen and inert gas, the inert gas flow rate is 180-200sccm, and the oxygen flow rate accounts for 0.15-6% of the total gas flow rate; The inert gas includes at least one of Ar, He, Ne, Ar, Kr, Xe, and Rn.

13. The preparation method according to claim 11, characterized in that The metal layer is deposited by DC magnetron sputtering, and the deposition parameters include: film forming power of 180~220W, sputtering pressure of 0.3~0.4Pa; the deposition atmosphere includes argon and nitrogen, and the volume ratio of the argon and the nitrogen is 95:5~97:3; the flow rate of argon in the deposition atmosphere is 120~140sccm, and the flow rate of nitrogen is 4~5sccm.

14. A perovskite battery, characterized in that: The flexible transparent conductive film comprises the flexible transparent conductive film according to any one of claims 1 to 9.

15. Use of the flexible transparent conductive film according to any one of claims 1 to 9 in touch panels, flexible thin-film photovoltaics and wearable display devices.

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