Flexible transparent conductive films, their preparation methods and applications, and perovskite solar cells

Abstract

This invention discloses a flexible transparent conductive film, its preparation method, and its applications, as well as perovskite solar cells, relating to the field of transparent conductive film technology. By employing a multi-layer electrode structure, where the metal oxide layer in the multi-layer electrode layer comprises oxides of at least three metals selected from Ti, Nb, Zn, Sn, In, W, and Al, this multi-metal doping imparts excellent conductivity and high light transmittance to the metal oxide layer, while simultaneously addressing the high brittleness of the metal oxide layer. The increased flexibility of the metal oxide layer ensures its stability in use. Furthermore, by doping the Ag in the metal layer with metals such as Bi, Pd, Cu, Nd, In, Sn, and Sb, the three-dimensional growth trend of Ag can be suppressed, allowing the metal layer to achieve excellent conductivity with a relatively thin thickness, thus solving the problem of simultaneously achieving high conductivity and high light transmittance in the metal layer.

Description

Technical Field

[0001] This invention relates to the field of transparent conductive film technology, and more specifically, to a flexible transparent conductive film, its preparation method and application, and perovskite solar cells. Background Technology

[0002] Transparent conductive film is a material that combines light transmittance and conductivity, and 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 the advantage of high light transmittance of about 90%, but their conductivity and flexibility are poor and they are brittle. After long-term use, they are prone to cracking or peeling off from the surrounding film layer due to repeated bending or thermal stress and other external factors.

[0003] Dielectric / metal / dielectric (DMD) multilayer electrode structures are considered a potential alternative to ITO electrodes in flexible perovskite solar cells (PSCs) due to their extremely high conductivity, excellent mechanical flexibility, and good light transmittance. However, current multilayer electrode structures still use materials such as ITO, FTO, and AZO as dielectrics, and the aforementioned drawbacks remain unresolved. Furthermore, the metal layer between the two dielectric layers presents a challenge in simultaneously achieving both conductivity (requiring sufficient thickness and uniformity) and light transmittance (requiring sufficient thinness).

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a flexible transparent conductive film, its preparation method and application, and perovskite batteries.

[0006] This invention is implemented as follows:

[0007] In a first aspect, the present invention 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, wherein the metal layer is located between two adjacent metal oxide layers.

[0008] The materials of the metal oxide layer include a first metal oxide and a second metal oxide.

[0009] The first metal oxide includes at least one of indium tin oxide, ZnO-doped In2O3, WO3-doped In2O3, and Al2O3-doped ZnO.

[0010] The second metal oxide includes at least one of TiO2, SnO2, ZnO and Nb2O5.

[0011] Preferably, the molar ratio of the first metal oxide to the second metal oxide is 65:35 to 90:10.

[0012] The materials of the metal layer include Ag and doped metals, and the doped metals include at least one of Bi, Pd, Cu, Nd, In, Sn and Sb.

[0013] In an optional embodiment, the materials of the metal oxide layer, in molar percentage, include: 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%.

[0014] Preferably, the material of the metal oxide layer includes any of the following combinations:

[0015] 1) Calculated by molar percentage, including ZnO doped In2O3: 65~75 mol%, TiO2: 10~15 mol%, and Nb2O5: 18~22 mol%.

[0016] 2) Calculated by molar percentage, including WO3-doped In2O3: 65~75 mol%, SnO2: 10~15 mol%, and ZnO: 18~22 mol%.

[0017] 3) Calculated by molar percentage, including Al2O3-doped ZnO: 65~75 mol%, TiO2: 10~15 mol%, and Nb2O5: 18~22 mol%.

[0018] In an optional embodiment, the mass ratio of In2O3 to ZnO in ZnO doped with In2O3 is 89:11 to 92:8.

[0019] In WO3-doped In2O3, the mass ratio of In2O3 to WO3 is 99.2:0.8 to 99.8:0.2.

[0020] In Al2O3-doped ZnO, the mass ratio of ZnO to Al2O3 is 97.5:2.5 to 98.5:1.5.

[0021] In indium tin oxide, the mass ratio of In2O3 to SnO2 is 89:11 to 92:8.

[0022] In an optional embodiment, the mass ratio of Ag to doped metal in the metal layer is 95:5 to 99.7:0.3.

[0023] Preferably, the metal doped in the metal layer is Bi and / or Pd.

[0024] Preferably, the mass ratio of Ag, Pd and Bi in the metal layer is 96:0.2:3.8 to 97:0.8:3.2.

[0025] 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.

[0026] In an optional embodiment, the material of the transparent substrate layer includes at least one of polyethylene terephthalate, polyimide, polyethylene naphthalate, polytetrafluoroethylene, ultrathin glass, or aluminum nitride transparent ceramic.

[0027] In a second aspect, the present invention provides a method for preparing a flexible transparent conductive film as described in the foregoing embodiments, comprising depositing a multilayer electrode layer on one side of a transparent substrate layer.

[0028] Preferably, the deposition method of the multilayer electrode layer includes at least one of electron beam vacuum deposition, magnetron sputtering, or ion plating.

[0029] Preferably, the metal layer deposition process includes 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.

[0030] The metal layer was deposited using DC magnetron sputtering. The deposition parameters included: film power of 180~220W, sputtering pressure of 0.3~0.4Pa, argon flow rate of 120~140sccm, and nitrogen flow rate of 4~5sccm.

[0031] In an optional embodiment, the metal oxide layer is deposited using DC magnetron sputtering. The deposition parameters include: a film-forming power of 420~480W, a sputtering pressure of 0.4~0.6Pa, and a sputtering temperature of 70~140℃. The deposition atmosphere includes oxygen and inert gas, with an inert gas flow rate of 180~200sccm and an oxygen flow rate accounting for 0.15~6% of the total gas flow rate.

[0032] Inert gases include at least one of Ar, He, Ne, Kr, Xe, and Rn.

[0033] Thirdly, the present invention provides a perovskite battery, including a flexible transparent conductive film as described in the foregoing embodiments.

[0034] Fourthly, the present invention provides an application of the flexible transparent conductive film as described above in touch panels, flexible thin-film photovoltaics, and wearable display devices.

[0035] The present invention has the following beneficial effects:

[0036] This invention provides a flexible transparent conductive film, its preparation method, and its applications in perovskite solar cells. By employing a multi-layer electrode structure, where the metal oxide layer in the multi-layer electrode layer comprises oxides of at least three metals selected from Ti, Nb, Zn, Sn, In, W, and Al, this multi-metal doping imparts excellent conductivity and high light transmittance to the metal oxide layer. Simultaneously, it overcomes the high brittleness of the metal oxide layer, improving its flexibility and ensuring its stability in use. Furthermore, by doping the Ag layer with metals such as Bi, Pd, Cu, Nd, In, Sn, and Sb, the three-dimensional growth tendency of Ag can be suppressed, allowing the metal layer to achieve excellent conductivity with a relatively thin thickness, thus solving the problem of simultaneously achieving high conductivity and high light transmittance in the metal layer. Attached Figure Description

[0037] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0038] Figure 1 This is a schematic diagram of the structure of the flexible transparent conductive film provided in Embodiment 1 of the present invention;

[0039] Figure 2 An atomic force microscope (AFM) image of the metal layer of the flexible transparent conductive film provided in Embodiment 2 of the present invention;

[0040] Figure 3 An atomic force microscope (AFM) image of the metal layer of the flexible transparent conductive film provided in Comparative Example 1 of this invention;

[0041] Figure 4 The absorption spectrum of the metal layer of the flexible transparent conductive film provided in Test Example 6 of the present invention;

[0042] Figure 5 The absorption spectrum of the metal layer of the IWO / Ag / IWO transparent conductive film provided in Test Example 6 of the present invention.

[0043] Icons: 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 Implementation

[0044] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0045] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0046] In a first aspect, the present invention 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, wherein the metal layer is located between two adjacent metal oxide layers.

[0047] Common multilayer electrode layers typically consist of a sandwich structure formed by two metal oxide layers and a metal layer between them, i.e., a dielectric / metal / dielectric (DMD) multilayer structure. Therefore, the multilayer electrode layer provided by this invention also has two metal oxide layers. In other embodiments, the number of metal oxide layers and metal layers can be adjusted as needed, as long as the performance of the flexible transparent conductive film can be guaranteed.

[0048] The materials of the metal oxide layer include at least three of the following: oxides of Ti, oxides of Nb, oxides of Zn, oxides of Sn, oxides of In, oxides of W, and oxides of Al.

[0049] The materials of the metal layer include Ag and doped metals, and the doped metals include at least one of Bi, Pd, Cu, Nd, In, Sn and Sb.

[0050] By employing a multi-layer electrode structure, where the metal oxide layer within the multi-layer electrode layer comprises oxides of at least three metals selected from Ti, Nb, Zn, Sn, In, W, and Al, this multi-metal doping imparts excellent conductivity and high light transmittance to the metal oxide layer. Simultaneously, it overcomes the high brittleness of metal oxide layers, improving their flexibility and ensuring stability in use. Furthermore, by doping the Ag layer with metals such as Bi, Pd, Cu, Nd, In, Sn, and Sb, the three-dimensional growth tendency of Ag can be suppressed, allowing the metal layer to achieve excellent conductivity with a relatively thin thickness, thus resolving the dilemma of simultaneously achieving high conductivity and high light transmittance in metal layers.

[0051] The material of the metal layer provided by the present invention can be, for example, 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.

[0052] Preferably, the mass ratio of Ag to doped metal in the metal layer is 95:5 to 99.7:0.3. That is, the mass percentage of Ag in the metal layer can be any value or a range between any two of 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, and 99.7wt%, with the balance being doped metal.

[0053] The structure of the metal layer is closely related to the performance of the flexible transparent conductive film. Only when the metal layer is thick enough can it achieve a permeation state to establish sufficient electrical pathways, thus ensuring that the flexible transparent conductive film has good conductivity. At the same time, the metal layer also needs to be thin enough to obtain its high optical transmittance.

[0054] The inventors discovered that the growth process of metal in a metal layer on the surface of a metal oxide layer includes several stages: nucleation, aggregation, and thickness increase. The material composition and surface properties of the metal oxide layer, as well as the material of the metal layer and various parameters during the deposition process, all affect the quality of the metal layer.

[0055] For example, during nucleation, the growth of metal in a metal layer depends on the dominant forces between adjacent metal atoms, or the dominant forces between metal atoms and atoms in the metal oxide layer. The metal growth mode switches between the Volmer-Weber mode and the Frank–van der Merwe mode, and its surface morphology tends to change from isolated three-dimensional atomic islands to a continuous, flat thin-film structure. When metal growth is dominated by the Volmer-Weber mode, the formed metal island structure induces localized surface plasmon resonance, which absorbs light in specific wavelengths, leading to a decrease in the transmittance of the electrode. Therefore, to obtain a metal layer with a smooth surface morphology and good photoelectric properties, it is necessary to suppress the Volmer-Weber growth mode.

[0056] From the perspective of the material of the metal layer, the present invention improves 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 into the metal Ag, thereby reducing the thickness and grain size of the Ag layer and facilitating the acquisition of Ag thin films. At the same time, the doping of bismuth can also suppress the three-dimensional growth of Ag, enabling the metal layer provided by the present invention to achieve better conductivity with a thinner thickness, and significantly improving the overall performance of the flexible transparent conductive film.

[0057] Therefore, preferably, the metal doped in the metal layer is Bi and / or Pd; the material of the metal layer may be, for example, Bi-doped Ag (Ag-Bi), Pd-doped Ag (Ag-Pd), or Bi and Pd co-doped Ag (Ag-Pd-Bi).

[0058] More preferably, the material of the metal layer is Bi-doped Ag metal (Ag-Bi) or Bi and Pd co-doped Ag metal (Ag-Pd-Bi); more preferably, it is Bi and Pd co-doped Ag metal (Ag-Pd-Bi).

[0059] In an optional embodiment, the mass ratio of Ag, Pd and Bi in the metal layer is 95:0.2:3.8 to 99.7:0.8:3.2.

[0060] From the perspective of material composition and surface properties of metal oxide layers, this invention uses at least three metal oxides selected from Ti, Nb, Zn, Sn, In, W and Al to prepare metal oxide layers, which can improve the brittleness of traditional metal oxides (ITO, FTO and AZO), which is beneficial for preparing flexible transparent conductive films. At the same time, the surface properties of metal oxide layers obtained by doping with multiple metal oxides are excellent, which is suitable for metal growth on their surface, thereby ensuring the comprehensive performance of flexible transparent conductive films.

[0061] The specific material selection for the metal oxide layer provided in this embodiment of the invention is as follows:

[0062] The materials of the metal oxide layer include a first metal oxide and a second metal oxide.

[0063] The first metal oxide is a bimetallic doped oxide, including at least one of indium tin oxide (ITO), ZnO-doped In2O3 (IZO), WO3-doped In2O3 (IWO), and Al2O3-doped ZnO (AZO).

[0064] The first metal oxide is preferably doped before being mixed with the second metal oxide. In other embodiments, each metal oxide in the first metal oxide may also be mixed together with the second metal oxide.

[0065] The second metal oxide is an oxide of a single metal, including at least one of TiO2, SnO2, ZnO, and Nb2O5.

[0066] By doping a first metal oxide with at least one second metal oxide, the properties of the first metal oxide can be significantly improved. For example, doping with TiO2 can increase the refractive index of the metal oxide layer, thereby improving the light transmittance of the flexible transparent conductive film; when the flexible transparent conductive film is bent, the metal oxide layer doped with SnO2 and Nb2O5 can suppress cracking and improve the bending resistance of the flexible transparent conductive film; when doped with ZnO, the conductivity of the metal oxide layer is enhanced.

[0067] Preferably, the molar ratio of the first metal oxide to the second metal oxide is 65:35 to 90:10.

[0068] That is, the molar percentage of the first metal oxide in the metal oxide layer can be any value among 65mol%, 70mol%, 75mol%, 80mol%, 85mol%, and 90mol%, or any range between two values, with the remainder being the second metal oxide.

[0069] Preferably, the material of the metal oxide layer, in molar percentage, comprises a first metal oxide: 65-75 mol%, TiO2 or 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.

[0070] When the TiO2 content is below 10 mol%, the barrier properties of the metal oxide layer against environmental substances such as moisture decrease, and the resistivity and transmittance deteriorate over time. Furthermore, since Ti also increases the refractive index of the metal oxide layer, a low Ti content cannot improve the refractive index. When the metal layer thickness is large, the suppression of hue changes in transmitted light is incomplete, leading to poor color reproducibility. When the TiO2 content is above 15 mol%, the content of other metal oxides is low, resulting in poor performance of the metal oxide layer.

[0071] When the SnO2 content is less than 10 mol%, the metal oxide layer is amorphous, which increases the probability of cracking during bending and reduces its bending resistance; when the SnO2 content is higher than 15 mol%, the content of other metal oxides is less, and the performance of the metal oxide layer is poor.

[0072] When the ZnO content is less than 15 mol%, the conductivity of the metal oxide layer decreases, and the surface sheet resistance stability of the metal oxide layer decreases; when the ZnO content is higher than 22 mol%, the content of other metal oxides is less, and the performance of the metal oxide layer is poor.

[0073] When the Nb2O5 content is less than 15 mol%, the metal oxide layer is amorphous, which increases the probability of cracking during bending and reduces its bending resistance; when the Nb2O5 content is higher than 22 mol%, the content of other metal oxides is less, and the performance of the metal oxide layer is poor.

[0074] Preferably, the material of the metal oxide layer includes any of the following combinations:

[0075] 1) In molar percentage, including ZnO doped with In2O3 (i.e. IZO): 65~75 mol%, TiO2: 10~15 mol%, and Nb2O5: 18~22 mol%; more preferably IZO: 68 mol%, TiO2: 12 mol%, and Nb2O5: 20 mol%.

[0076] 2) Calculated by molar percentage, including WO3 doped In2O3 (i.e., IWO) 65~75 mol%, SnO2 10~15 mol%, and ZnO 18~22 mol%.

[0077] 3) Calculated by molar percentage, including 65~75 mol% Al2O3-doped ZnO (i.e., AZO), 10~15 mol% TiO2, and 18~22 mol% Nb2O5.

[0078] By selecting any of the above three combinations to form a metal oxide layer, both its conductivity and light transmittance are excellent, and it is beneficial for the metal layer to grow into a uniform and thin film, thereby improving the overall performance of the flexible transparent conductive film.

[0079] In an optional embodiment, in ZnO doped with In2O3 (IZO), the mass ratio of In2O3 to ZnO is 89:11 to 92:8, preferably 90:10.

[0080] In WO3-doped In2O3 (IWO), the mass ratio of In2O3 to WO3 is 99.2:0.8 to 99.8:0.2, preferably 99.5:0.5.

[0081] In Al2O3-doped ZnO (AZO), the mass ratio of ZnO to Al2O3 is 97.5:2.5 to 98.5:1.5, preferably 98:2.

[0082] In indium tin oxide (ITO), the mass ratio of In2O3 to SnO2 is 89:11 to 92:8, preferably 90:10.

[0083] By controlling the content of each metal oxide in the first metal oxide, namely ITO, IWO, IZO and AZO, within the above-mentioned range, it is possible to ensure that the conductivity and light transmittance of the metal oxide layer are both good.

[0084] In optional embodiments, the thickness of the metal layer is 1~15nm, preferably 3~12nm, and more preferably 4~10nm. When the thickness of the metal layer is less than 1nm, the control precision of the metal layer preparation process is required to be high, the preparation is difficult, and the conductivity is poor; when the thickness of the metal layer is greater than 15nm, the transmittance of the metal layer is poor.

[0085] 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 optical interference effect of the metal oxide layer in converting reflected light generated in the metal thin film into transmitted light may deviate from the optimal conditions, resulting in poor light transmittance.

[0086] In optional embodiments, the transparent substrate layer is made of at least one of polyethylene terephthalate (PET), polyimide (PI), polyethylene naphthalate (PEN), polytetrafluoroethylene (PTFE), ultrathin glass (UTG), or aluminum nitride transparent ceramic (ALON). Polyethylene naphthalate (PEN) is preferred.

[0087] In a second aspect, the present invention provides a method for preparing a flexible transparent conductive film as described in the foregoing embodiments, comprising depositing a multilayer electrode layer on one side of a transparent substrate layer.

[0088] Because Ag has poor bonding ability with existing metal oxide materials such as ITO, FTO and AZO, 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 requires an additional number of sputtering targets, increasing equipment and production costs, but also the Cu layer is too thin, only 0.1 nm thick, which requires a very high film formation process and is difficult to control. This makes it difficult to control the stability of the prepared flexible transparent conductive film in terms of sheet resistance and transmittance.

[0089] The flexible transparent conductive film provided by this invention does not require additional copper or other metal seed layers, thus not increasing manufacturing costs. At the same time, the appropriate thickness of the metal layer makes its deposition operation simple and easy to control, which helps to ensure the surface sheet resistance stability and transmittance stability of the flexible transparent conductive film. Furthermore, with the material selection of this invention, a flexible transparent conductive film with low surface sheet resistance and high transmittance can be obtained.

[0090] Preferably, the deposition method of the multilayer electrode layer includes at least one of electron beam vacuum deposition, magnetron sputtering or ion plating, with magnetron sputtering being the preferred method.

[0091] Preferably, the metal layer deposition process includes using a mixed atmosphere of argon and nitrogen as the deposition atmosphere, with a volume ratio of argon to nitrogen of 95:5 to 97:3. Incorporating trace amounts of nitrogen during metal layer deposition not only further enhances the wettability of Ag on the metal oxide layer surface but also better suppresses the Volmer-Weber growth mode of the metal during film formation. This ensures that while reducing the metal layer thickness, good light transmittance, conductivity, and bending resistance are still maintained.

[0092] The metal layer was deposited using DC magnetron sputtering. The deposition parameters included: a film deposition 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 metal layer preparation parameters within the above range, a metal layer with uniform morphology, thin thickness, and good adhesion to the metal oxide layer could be obtained.

[0093] Since the metal layer is a material composed of Ag and doped metal, it is preferable to first mix Ag and doped metal in a certain proportion to prepare an alloy target, and then use the alloy target for DC magnetron sputtering deposition. In other embodiments, pure silver target and pure metal target with doped metal can also be used separately for magnetron sputtering deposition in a certain proportion.

[0094] In an optional embodiment, the metal oxide layer is deposited using DC magnetron sputtering. The deposition parameters include: a film-forming power of 420~480W, a sputtering pressure of 0.4~0.6Pa, and a sputtering temperature of 70~140℃. The deposition atmosphere includes oxygen and inert gas, with an inert gas flow rate of 180~200sccm and an oxygen flow rate accounting for 0.15~6% of the total gas flow rate.

[0095] The inert gas includes at least one of Ar, He, Ne, Ar, Kr, Xe and Rn, preferably argon (Ar).

[0096] 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, ensuring the conductivity and light effect of the metal oxide layer, thereby obtaining a flexible transparent conductive film with better overall performance.

[0097] Thirdly, the present invention provides a perovskite battery, including a flexible transparent conductive film as described in the foregoing embodiments.

[0098] Fourthly, the present invention provides an application of the flexible transparent conductive film as described above in touch panels, flexible thin-film photovoltaics, and wearable display devices.

[0099] The meanings of the performance parameters and the testing methods for the flexible transparent conductive films / transparent conductive films provided in the following embodiments and comparative examples are as follows (the "sample" in the testing methods refers to the flexible transparent conductive film / transparent conductive film provided in the corresponding embodiments or comparative examples):

[0100] Tone evaluation

[0101] Color measurement, color difference analysis, and color quality evaluation were performed using a spectrophotometer. The evaluation results were displayed using the a* and b* values ​​in the L*a*b color table. When the a* and b* values ​​are within the range of -1 to 1, it is considered that the hue change is difficult to perceive by the human eye, which is the preferred condition. To ensure that the sample still has stable color reproducibility after long-term use, the closer the a* and b* values ​​are to zero, the better.

[0102] Transmittance testing

[0103] The average transmittance of a sample in the visible light range of 400nm to 800nm ​​is measured using a spectrophotometer. The principle is to decompose the light source into monochromatic light using a spectrophotometer (grating or prism), and then measure the transmitted light intensity of the sample wavelength by wavelength. A transmittance percentage closer to 100% is considered better.

[0104] Shear resistance stability test

[0105] A 4-probe sheet resistance meter was used for measurement. Ten different points were selected on the sample, and continuous measurements were taken for 15 seconds at each point. The average sheet resistance (R0) displayed at all measurement points was calculated. ave Then, based on these 10 square resistance values, according to (R) max -R min ) / R ave *Calculate the rate of change of surface sheet resistance (100%). A higher value indicates poorer conductivity of the film, while a lower value indicates better conductivity.

[0106] Environmental resistance test

[0107] The sample was placed in a constant temperature bath at 85℃ and 85%RH for 200 hours. The transmittance of the sample before and after the holding period was measured, and the decrease in transmittance was calculated based on "transmittance before holding - transmittance after holding". The surface sheet resistance (R1) before and after the holding period was measured, and the increase in surface sheet resistance was calculated based on "(R1-R2) / R2*100%". When the decrease in transmittance was less than 1% and the increase in surface sheet resistance was less than 10%, the environmental resistance of the sample was rated "A"; otherwise, it was rated "B". Samples rated "A" for environmental resistance, when applied to touch panels, can ensure long-term stable driving performance under their operating environment.

[0108] Bending test

[0109] The sample was wound around an 8mm diameter cylinder. The surface sheet resistance of the sample before and after bending was measured using a 4-probe sheet resistance meter. The surface sheet resistance before bending was recorded as R1, and the surface sheet resistance after bending was recorded as R3. The rate of change (rise) of the surface sheet resistance before and after bending was calculated using the formula "(R3-R1) / R1*100%". The smaller the rate of change, the better the sample's performance. Samples with a surface sheet resistance change rate less than 1.1% were rated "A", and the rest were rated "B". Samples rated "A" in the bending test can withstand the effects of repeated heating and extrusion during manufacturing processes, such as perovskite solar cells, and can also ensure the stable performance of the final product during use.

[0110] Example 1

[0111] Please refer to Figure 1 This embodiment provides a flexible transparent conductive film 100, including a transparent substrate layer 110 and a multilayer electrode layer 120 on its surface.

[0112] The transparent substrate 110 is made of polyethylene naphthalate (PEN) and has a thickness of 80 μm.

[0113] The multilayer electrode layer 120 is a sandwich structure consisting of two metal oxide layers and a metal layer 123 between the two metal oxide layers, wherein the first metal oxide layer 121 is tightly connected to the transparent substrate layer.

[0114] The two metal oxide layers are made of the same material, and the material of each metal oxide layer is expressed as a molar percentage, including WO3 doped In2O3 (IWO): 68 mol%, TiO2: 12 mol%, and Nb2O5: 20 mol%.

[0115] The metal layer consists of Ag: 96.5 wt%, Pd: 0.5 wt%, and Bi: 3 wt% by mass percentage.

[0116] This embodiment also provides a method for preparing the above-mentioned flexible transparent conductive film 100, including the following steps:

[0117] S01. Using polyethylene naphthalate (PEN) material with a thickness of 80 μm as a transparent substrate layer 110, a first metal oxide layer 121 is deposited on one side of the transparent substrate layer 110 by DC magnetron sputtering. The deposition parameters of the first metal oxide layer 121 include: a deposition atmosphere of argon and a small amount of oxygen, an argon flow rate of 190 sccm, an oxygen flow rate of 0.3 sccm, a film deposition power of 450 W, a sputtering pressure of 0.5 Pa, and a sputtering temperature of 70 °C. The thickness of the deposited first metal oxide layer 121 is 35 nm.

[0118] S02. A metal layer 123 is deposited on the surface of the first metal oxide layer 121 using DC magnetron sputtering. The deposition parameters for the metal layer 123 include: a deposition atmosphere 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 deposition power of 200 W, and a sputtering pressure of 0.36 Pa. The thickness of the deposited metal layer 123 is 8 nm.

[0119] S03. A second metal oxide layer 122 is deposited on the surface of the metal layer 123 using DC magnetron sputtering. The deposition parameters for 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 deposition 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.

[0120] Example 2

[0121] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 1 is that the sputtering temperature of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 is 100°C.

[0122] The metal layer 123 deposited in this embodiment was observed under an atomic force microscope (AFM), and the results were as follows: Figure 2 The results show that the root mean square roughness (Sq) of the surface is analyzed based on its surface morphology, and the Sq is 6.41. The small particle size indicates that the three-dimensional growth mode of Ag is suppressed, which can achieve the effect of high transmittance and surface sheet resistance at a low thickness.

[0123] Example 3

[0124] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 1 is that the sputtering temperature of the first metal oxide layer 121 and the second metal oxide layer 122 is 120°C.

[0125] Example 4

[0126] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 1 is that the sputtering temperature of the first metal oxide layer 121 and the second metal oxide layer 122 is 140°C.

[0127] Example 5

[0128] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 1 is that the materials of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 are a mixture of indium tin oxide (ITO), niobium oxide (Nb2O5) and titanium oxide (TiO2).

[0129] In ITO, the molar ratio of indium oxide (In2O3) to tin oxide (SnO2) is 90:10; and the molar ratio of ITO, Nb2O5 and TiO2 is 65:20:15.

[0130] That is, the molar amount of indium tin oxide (ITO) is 65 mol, the molar amount of niobium oxide (Nb2O5) is 20 mol, and the molar amount of titanium oxide (TiO2) is 15 mol.

[0131] Example 6

[0132] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 5 is that the sputtering temperature of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 is 100°C.

[0133] Example 7

[0134] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 5 is that the sputtering temperature of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 is 120°C.

[0135] Example 8

[0136] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 5 is that the sputtering temperature of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 is 140°C.

[0137] Example 9

[0138] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 5 only in that the molar ratio of ITO, Nb2O5 and TiO2 is 90:6:4.

[0139] That is, the molar amount of indium tin oxide (ITO) is 90 mol, the molar amount of niobium oxide (Nb2O5) is 6 mol, and the molar amount of titanium oxide (TiO2) is 4 mol.

[0140] Example 10

[0141] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 1 is that the materials of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 are a mixture of ZnO-doped In2O3 (IZO), niobium oxide (Nb2O5) and titanium oxide (TiO2).

[0142] In IZO, the molar ratio of indium oxide (In2O3) to zinc oxide (ZnO) is 95:5; and the molar ratio of IZO, Nb2O5 and TiO2 is 65:20:15.

[0143] That is, the molar amount of indium tin oxide (IZO) is 65 mol, the molar amount of niobium oxide (Nb2O5) is 20 mol, and the molar amount of titanium oxide (TiO2) is 15 mol.

[0144] Example 11

[0145] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 10 is that the sputtering temperature of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 is 100°C.

[0146] Example 12

[0147] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 10 is that the sputtering temperature of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 is 120°C.

[0148] Example 13

[0149] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 10 is that the sputtering temperature of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 is 140°C.

[0150] Example 14

[0151] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Example 10 only in that the molar ratio of IZO, Nb2O5 and TiO2 is 90:6:4.

[0152] That is, the molar amount of indium tin oxide (IZO) is 90 mol, the molar amount of niobium oxide (Nb2O5) is 6 mol, and the molar amount of titanium oxide (TiO2) is 4 mol.

[0153] Comparative Example 1

[0154] This comparative example provides a transparent conductive film whose structure differs from that of Example 2 only in that: the metal oxide layer is made of ITO material, with Sn:In2O3 = 90:10 in ITO; and the metal layer is made of pure silver material.

[0155] This comparative example also provides a method for preparing the above-mentioned transparent conductive film, which differs from Example 2 only in that the deposition atmosphere in step S02 is 100wt% argon.

[0156] The metal layer 123 obtained by this comparative deposition was observed under an atomic force microscope (AFM), and the results were as follows: Figure 3 The results show that the root mean square roughness (Sq) of the surface is 16.7, indicating that the particle size is relatively large and the Ag layer tends to grow in the thickness direction.

[0157] Comparative Example 2

[0158] This comparative example provides a transparent conductive film whose structure differs from that of Example 3 only in that: the metal oxide layer is made of ITO material, with Sn:In2O3 = 90:10 in ITO; and the metal layer is made of pure silver material.

[0159] This comparative example also provides a method for preparing the above-mentioned transparent conductive film, which differs from Example 3 only in that the deposition atmosphere in step S02 is 100wt% argon.

[0160] Comparative Example 3

[0161] This comparative example provides a transparent conductive film whose structure differs from that of Example 4 only in that: the metal oxide layer is made of ITO material, with Sn:In2O3 = 90:10 in ITO; and the metal layer is made of pure silver material.

[0162] This comparative example also provides a method for preparing the above-mentioned transparent conductive film, which differs from Example 4 only in that the deposition atmosphere in step S02 is 100wt% argon.

[0163] Experimental Example 1

[0164] The flexible transparent conductive films provided in Examples 1-9 and the transparent conductive films provided in Comparative Examples 1-3 were subjected to color tone evaluation, transmittance detection, sheet resistance stability detection, environmental resistance detection, and bending detection, and the results are shown in Table 1.

[0165] Table 1. Properties of Flexible Transparent Conductive Films and Transparent Conductive Films

[0166]

[0167] Referring to the data in Table 1, Comparative Examples 1-3, which used a multilayer electrode structure of ITO / Ag / ITO to prepare transparent conductive films, exhibited relatively large values ​​for parameters a* and b*, resulting in poor color reproduction, low transmittance, high surface sheet resistance, and poor environmental resistance and flexibility. This indicates that the traditional ITO / Ag / ITO multilayer electrode structure is insufficient to meet the high-performance requirements of transparent conductive films. In contrast, the a* and b* values ​​of the embodiments of this invention are closer to 0 than those of the comparative examples. The flexible transparent conductive film exhibits excellent color reproduction, high transmittance, low surface sheet resistance, and excellent environmental resistance and flexibility, demonstrating superior and more stable performance.

[0168] Furthermore, as can be seen from Examples 1-4, Examples 5-8, Examples 10-13 and Comparative Examples 1-3, as the sputtering temperature of the metal oxide layer increases, the performance of the flexible transparent conductive film also shows significant differences. The transmittance increases with the increase of sputtering temperature, while the surface sheet resistance decreases with the increase of sputtering temperature.

[0169] As can be seen from Examples 9 and 14, the flexible transparent conductive films obtained after ITO and IZO substitution have comparable performance, with good light transmittance and low surface sheet resistance, as well as good environmental resistance and excellent application value.

[0170] Example 15

[0171] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 4 only in that the thickness of the metal layer 123 is 6 nm.

[0172] Example 16

[0173] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 15 is that in step S02, the deposition atmosphere for the metal layer deposition is 100wt% argon.

[0174] Example 17

[0175] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 4 only in that the thickness of the metal layer 123 is 7 nm.

[0176] Example 18

[0177] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 4 only in that the thickness of the metal layer 123 is 9 nm.

[0178] Comparative Example 4

[0179] This comparative example provides a transparent conductive film with the same structure as Comparative Example 1. The only difference between the two examples is that the thickness of the metal layer 123 is 6 nm.

[0180] Comparative Example 5

[0181] This comparative example provides a transparent conductive film with the same structure as Comparative Example 1. The only difference between the two examples is that the thickness of the metal layer 123 is 7 nm.

[0182] Comparative Example 6

[0183] This comparative example provides a transparent conductive film with the same structure as Comparative Example 1. The only difference between the two examples is that the thickness of the metal layer 123 is 9 nm.

[0184] Experimental Example 2

[0185] The flexible transparent conductive films provided in Examples 15-18 and the transparent conductive films provided in Comparative Examples 4-6 were subjected to color tone evaluation, transmittance testing, sheet resistance stability testing, environmental resistance testing, and bending testing, and the results are shown in Table 2.

[0186] Table 2. Properties of Flexible Transparent Conductive Films and Transparent Conductive Films

[0187]

[0188] Referring to the data in Table 2, Comparative Example 4 has better color reproduction and better transmittance, but has a larger surface sheet resistance and poorer environmental resistance; Comparative Example 5 has better color reproduction, poorer transmittance, and a larger surface sheet resistance, resulting in poorer environmental resistance; Comparative Example 6 has a reduced surface sheet resistance, but has poorer color reproduction, poorer transmittance, and poorer environmental resistance.

[0189] This demonstrates that the transparent conductive film prepared by the traditional ITO / Ag / ITO multilayer electrode layer structure cannot achieve both high transmittance (88.6% in Comparative Example 4) and low surface sheet resistance (8.3 Ω / hole in Comparative Example 6), while Example 17 of the present invention can achieve both high transmittance (90.6%) and low surface sheet resistance (9.7 Ω / hole), and the overall performance of the flexible transparent conductive film is better.

[0190] Example 19

[0191] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 4 only in that the thickness of the first metal oxide layer 121 is 40 nm.

[0192] Example 20

[0193] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 4 only in that the thickness of the first metal oxide layer 121 is 30 nm.

[0194] Example 21

[0195] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 4 only in that the thickness of the first metal oxide layer 121 is 20 nm.

[0196] Example 22

[0197] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 4 only in that the thickness of the first metal oxide layer 121 is 15 nm.

[0198] Experimental Example 3

[0199] The flexible transparent conductive films provided in Examples 19-22 were subjected to color tone evaluation, transmittance testing, sheet resistance stability testing, environmental resistance testing, and bending testing, and the results are shown in Table 3.

[0200] Table 3 Performance of Flexible Transparent Conductive Films

[0201]

[0202] Referring to the data in Table 3, as the thickness of the first metal oxide layer 121 increases, both the surface sheet resistance and transmittance of the flexible transparent conductive film decrease slightly. Specifically, when the thickness of the first metal oxide layer 121 is 30-40 nm, the a* and b* values ​​for hue evaluation are relatively small, indicating better color reproduction and stable transmittance.

[0203] Example 23

[0204] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 2 is that the prepared flexible transparent conductive film is annealed at a temperature of 100°C for 30 minutes.

[0205] Example 24

[0206] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 2 is that the prepared flexible transparent conductive film is annealed at a temperature of 150°C for 30 minutes.

[0207] Example 25

[0208] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 2 is that the prepared flexible transparent conductive film is annealed at a temperature of 200°C for 30 minutes.

[0209] Example 26

[0210] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 3 is that the prepared flexible transparent conductive film is annealed at a temperature of 100°C for 30 minutes.

[0211] Example 27

[0212] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 3 is that the prepared flexible transparent conductive film is annealed at a temperature of 150°C for 30 minutes.

[0213] Example 28

[0214] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 3 is that the prepared flexible transparent conductive film is annealed at a temperature of 200°C for 30 minutes.

[0215] Example 29

[0216] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 4 is that the prepared flexible transparent conductive film is annealed at a temperature of 100°C for 30 minutes.

[0217] Example 30

[0218] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 4 is that the prepared flexible transparent conductive film is annealed at a temperature of 150°C for 30 minutes.

[0219] Example 31

[0220] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 4 is that the prepared flexible transparent conductive film is annealed at a temperature of 200°C for 30 minutes.

[0221] Test Example 4

[0222] The flexible transparent conductive films provided in Examples 23-31 were subjected to color tone evaluation, transmittance testing, sheet resistance stability testing, environmental resistance testing, and bending testing, and the results are shown in Table 4.

[0223] Table 4 Performance of Flexible Transparent Conductive Films

[0224]

[0225] Referring to the data in Table 4, the flexible transparent conductive film provided in the embodiments of the present invention, after annealing, not only does its performance not decrease, but it also promotes the crystallinity of the metal oxide layer, improves the conductivity and transmittance of the oxide layer, and the surface sheet resistance of the flexible transparent conductive film decreases as the annealing temperature of the flexible transparent conductive film increases. Moreover, when the sputtering temperature of the metal oxide layer is 140°C and the annealing temperature is 150~200°C (i.e., Examples 30 and 31), the overall performance of the flexible transparent conductive film is optimal.

[0226] Example 32

[0227] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 19 is that the material of the metal layer 123, by mass percentage, includes Ag: 99.5wt% and Pd: 0.5wt%.

[0228] Example 33

[0229] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 20 only in that: the material of the metal layer 123, by mass percentage, includes Ag: 97wt% and Bi: 3wt%.

[0230] Example 34

[0231] This embodiment provides a flexible transparent conductive film and its preparation method. The only difference from Embodiment 1 is that the materials of the first metal oxide layer 121 in step S01 and the second metal oxide layer 122 in step S02 are a mixture of WO3-doped In2O3 (IWO), tin oxide (SnO2) and zinc oxide (ZnO).

[0232] In IWO, the molar ratio of tungsten oxide (WO3) to indium oxide (In2O3) is 99.2:0.8; and the molar ratio of IWO, SnO2 and ZnO is 65:15:20.

[0233] That is, the molar amount of WO3 doped with In2O3 (IWO) is 65 mol, the molar amount of tin oxide (SnO2) is 15 mol, and the molar amount of zinc oxide (ZnO) is 20 mol.

[0234] Example 35

[0235] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 34 only in that the molar ratio of IWO, SnO2 and ZnO is 70:12:18.

[0236] That is, the molar amount of WO3 doped with In2O3 (IWO) is 70 mol, the molar amount of tin oxide (SnO2) is 12 mol, and the molar amount of zinc oxide (ZnO) is 18 mol.

[0237] Example 36

[0238] This embodiment provides a flexible transparent conductive film and its preparation method, which differs from Embodiment 34 only in that the molar ratio of IWO, SnO2 and ZnO is 75:10:15.

[0239] That is, the molar amount of WO3 doped with In2O3 (IWO) is 75 mol, the molar amount of tin oxide (SnO2) is 10 mol, and the molar amount of zinc oxide (ZnO) is 15 mol.

[0240] Comparative Example 7

[0241] This comparative example provides a transparent conductive film with a structure similar to that of Example 22, the only difference being that the material of the metal layer is pure silver.

[0242] This comparative example also provides a method for preparing the above-mentioned transparent conductive film, which differs from Example 22 only in that the deposition atmosphere in step S02 is 100wt% argon.

[0243] Experimental Example 5

[0244] The flexible transparent conductive films / transparent conductive films provided in Examples 32-36 and Comparative Example 7 were subjected to color tone evaluation, transmittance testing, sheet resistance stability testing, environmental resistance testing, and bending testing, and the results are shown in Table 5.

[0245] Table 5 Performance of Flexible Transparent Conductive Film / Transparent Conductive Film

[0246]

[0247] Referring to the data in Table 5, the surface sheet resistance of Comparative Example 7 is significantly improved, but its overall performance is worse than that of the Example.

[0248] Experimental Example 6

[0249] A group of flexible transparent conductive films with different metal layer thicknesses were prepared according to the method of Example 17. The metal layer thicknesses were 3 nm, 5 nm, 7 nm, 9 nm and 11 nm.

[0250] Meanwhile, a group of IWO / Ag / IWO transparent conductive films were prepared according to the method of Comparative Example 5. The IWO / Ag / IWO transparent conductive films were flexible transparent conductive films with different metal layer thicknesses, namely 3nm, 5nm, 7nm, 9nm and 11nm.

[0251] The above-mentioned flexible transparent conductive film and IWO / Ag / IWO transparent conductive film were subjected to spectral analysis to obtain the following results: Figure 4 The results are shown in Figure 5.

[0252] Depend on Figure 5 It is known that the composite electrode prepared by the traditional IWO / Ag / IWO transparent conductive film only has good transmittance at a wavelength of 600nm, and the transmittance drops sharply after 600nm, resulting in a very narrow half-wave peak. Figure 4 In the present invention, the flexible transparent conductive film provided in the embodiments of the present invention has a higher transmittance at 600 nm after both the metal oxide layer and the metal layer are doped, and the transmittance thereafter decreases slowly, and its half-wave peak is wider.

[0253] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A flexible transparent conductive film, characterized in that, It includes a transparent substrate layer and a multilayer electrode layer on its surface; the multilayer electrode layer includes 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 includes at least one of indium tin oxide, ZnO-doped In2O3, WO3-doped In2O3, and Al2O3-doped ZnO; The second metal oxide includes at least two 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 oxide layer includes any of the following combinations: 1) Calculated as a molar percentage, including ZnO-doped In2O3: 65~75 mol%, TiO2: 10~15 mol%, and Nb2O5: 18~22 mol%; 2) Calculated as a percentage by molar, including WO3-doped In2O3: 65~75 mol%, SnO2: 10~15 mol%, and ZnO: 18~22 mol%; 3) Calculated as a molar percentage, including Al2O3-doped ZnO: 65~75 mol%, TiO2: 10~15 mol%, and Nb2O5: 18~22 mol%; The material of the metal layer comprises Ag and a doped metal in a mass ratio of 95:5 to 99.7:0.3, wherein the doped metal comprises at least one of Bi, Pd, Cu, Nd, In, Sn and Sb.

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

8.

3. The flexible transparent conductive film according to claim 1, characterized in that, The doped metal in the metal layer is Bi and / or Pd.

4. The flexible transparent conductive film according to claim 3, 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 to 97:0.8:3.

2.

5. The flexible transparent conductive film according to claim 1, characterized in that, The thickness of the metal layer is 1~15nm; and / or, the thickness of each metal oxide layer is 15~50nm.

6. The flexible transparent conductive film according to claim 1, characterized in that, The material of the transparent substrate layer includes at least one of polyethylene terephthalate, polyimide, polyethylene naphthalate, polytetrafluoroethylene, ultrathin glass, or aluminum nitride transparent ceramic.

7. A method for preparing a flexible transparent conductive film as described in any one of claims 1 to 6, characterized in that, This includes depositing the multilayer electrode layer on one side of the transparent substrate.

8. The preparation method according to claim 7, characterized in that, The deposition method of the multilayer electrode layer includes at least one of electron beam vacuum deposition, magnetron sputtering, or ion plating.

9. The preparation method according to claim 8, characterized in that, The metal oxide layer was deposited using DC magnetron sputtering. The deposition parameters included: a film-forming power of 420~480W, a sputtering pressure of 0.4~0.6Pa, and a sputtering temperature of 70~140℃. The deposition atmosphere consisted of oxygen and an inert gas, with the inert gas flow rate at 180~200 sccm and the oxygen flow rate accounting 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.

10. The preparation method according to claim 8, characterized in that, The metal layer is deposited using DC magnetron sputtering. The deposition parameters include: a film-forming power of 180~220W and a sputtering pressure of 0.3~0.4Pa; the deposition atmosphere includes argon and nitrogen, and the volume ratio of argon to 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.

11. A perovskite battery, characterized in that, Including the flexible transparent conductive film as described in any one of claims 1 to 6.

12. The application of a flexible transparent conductive film as described in any one of claims 1 to 6 in touch panels, flexible thin-film photovoltaics, and wearable display devices.

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