CN113707812B - Random metal grid ultrathin flexible transparent electrode, photovoltaic device and preparation method of random metal grid ultrathin flexible transparent electrode - Google Patents

Random metal grid ultrathin flexible transparent electrode, photovoltaic device and preparation method of random metal grid ultrathin flexible transparent electrode Download PDF

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CN113707812B
CN113707812B CN202110912598.1A CN202110912598A CN113707812B CN 113707812 B CN113707812 B CN 113707812B CN 202110912598 A CN202110912598 A CN 202110912598A CN 113707812 B CN113707812 B CN 113707812B
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CN113707812A (en
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朱瑞
吴疆
皇甫一鸣
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Yangtze River Delta Institute Of Optoelectronics Peking University
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    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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Abstract

The invention discloses a random metal grid ultrathin flexible transparent electrode, a photovoltaic device and a preparation method of the random metal grid ultrathin flexible transparent electrode. The method comprises the steps of forming a sacrificial layer with random cracks on a hard growth substrate, forming a metal layer on the surface of the sacrificial layer and on the hard growth substrate between gaps of the random cracks, removing the sacrificial layer, thickening metal to obtain a random metal grid, and preparing a flexible film; the flexible film and the random metal grid are taken off from the hard growth substrate together, so that the flat surface originally contacted with the hard growth substrate is exposed and is used as the surface of the flattened ultrathin flexible electrode; the invention effectively solves the problems of metal grid moire and surface roughness; the random metal grid is embedded into the flexible film, so that the thickness of the random metal grid is not limited any more, and the transparency can be ensured and the extremely high conductivity can be realized; meanwhile, the invention can realize an ultrathin (<5 mu m) ultra-light perovskite photovoltaic device with an ultra-high energy-mass ratio based on the transparent electrode.

Description

Random metal grid ultrathin flexible transparent electrode, photovoltaic device and preparation method of random metal grid ultrathin flexible transparent electrode
Technical Field
The invention relates to the field of photoelectric functional devices, in particular to a random metal grid ultrathin flexible transparent electrode, a photovoltaic device and a preparation method thereof.
Background
Transparent and conductive electrode materials are important in various photoelectric devices, and are widely applied to products such as photovoltaic cells, photoelectric detectors, liquid crystal displays and Light Emitting Diodes (LEDs). Indium Tin Oxide (ITO) is the most commonly used transparent electrode material at present, but due to its fragile rigidity and poor conductivity under high transparency, it does not perform well in large area application scenarios requiring high conductivity, especially large area flexible application scenarios.
In contrast, the metal grid has higher light transmittance and electrical conductivity, the transparency of the metal grid can be accurately regulated and controlled by the duty ratio, and the electrical conductivity can be accurately regulated and controlled by the duty ratio, the line width and the thickness; and the bending resistance of the metal grid on the flexible substrate is better than that of ITO. However, the metal grid usually suffers from large surface fluctuation, namely the grid area with metal is high in topography, the mesh area without metal is low in topography, the device topography is affected, and even short circuit is caused. And the traditional metal grid is a periodic grid, which introduces Moire problem and limits the application of the metal grid in displays, cameras and optical sensing components. In addition, the conventional grid electrode needs to be fabricated using a high-cost photolithography technique, resulting in a high price. Finally, the thickness of the traditional flexible electrode substrate is about 50-100 microns, and compared with an effective photoelectric functional layer with the thickness of about 1 micron, the electrode substrate has a large amount of invalid weight, so that the light weight and the energy-to-mass ratio of a device are not favorably improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a random metal grid ultrathin flexible transparent electrode, a photovoltaic device and a preparation method thereof, which can perfectly solve the problems of metal grid moire and surface planarization, and the thickness is less than 5 microns.
One object of the present invention is to propose a random metal grid ultrathin flexible transparent electrode and a photovoltaic device.
The random metal grid ultrathin flexible transparent electrode comprises: preparing and forming a sacrificial layer on a hard growth substrate; heating the sacrificial layer, and controlling the heating temperature and time to crack the sacrificial layer randomly to generate a gap; preparing metal on the sacrificial layer by a Physical Vapor Deposition (PVD) method, and forming a metal layer on the surface of the sacrificial layer and the hard growth substrate between the random cracking gaps; etching to remove the sacrificial layer, removing the metal layer grown on the sacrificial layer, and reserving the metal layer grown on the hard growth substrate so as to obtain a random metal grid template formed on the hard growth substrate; electroplating metal on the random metal grid template, and increasing the thickness to 700-900 nm to obtain a random metal grid; preparing a compact and uniform flexible film on a hard growth substrate with a random metal grid by adopting a Chemical Vapor Deposition (CVD) method; the flexible film and the random metal grid are taken off from the hard growth substrate together, so that the flat surface originally contacted with the hard growth substrate is exposed and is used as the surface of the flattened ultrathin flexible electrode.
The hard growth substrate adopts a glass substrate, a quartz substrate or a silicon substrate.
The sacrificial layer is made of metal oxide such as titanium oxide, aluminum oxide and zinc oxide.
The metal layer is made of metal which does not react with the perovskite material and is made of one or more alloy materials of gold (Au), silver (Ag), aluminum (Al), nickel (Ni) and titanium (Ti).
The flexible film adopts Parylene-C (poly 2-chloro-p-xylene), Parylene-D (poly 2, 5-dichloro-p-xylene), Parylene-N (Parylene), Parylene VT4 ( poly 2,3,5, 6-tetrafluoro-p-xylene), Parylene AF4 ( poly 1,1 ', 4, 4' -tetrafluoro-p-xylene) or Parylene AF8 ( poly 1,1 ', 2,3,4, 4', 5, 6-octafluoro-p-xylene).
The flexible photovoltaic device of the random metal grid flexible transparent electrode comprises: the flexible transparent electrode comprises a random metal grid flexible transparent electrode, a first transmission layer, a perovskite light absorption layer, a second transmission layer and a metal electrode; the surface of the flexible film without the random metal grid is stuck to the surface of the hard preparation substrate; for a flexible photovoltaic device with a formal structure, a first transmission layer is an electron transmission layer, a second transmission layer is a hole transmission layer, and the electron transmission layer, the perovskite light absorption layer, the hole transmission layer and the metal electrode are sequentially grown on the random metal grid flexible transparent electrode; or, for the flexible photovoltaic device with the trans-structure, the first transmission layer is a hole transmission layer, the second transmission layer is an electron transmission layer, and the hole transmission layer, the perovskite light absorption layer, the electron transmission layer and the metal electrode are sequentially grown on the random metal grid flexible transparent electrode.
The perovskite light absorption layer is preferably made of an organic-inorganic perovskite material.
The invention also aims to provide a preparation method of the random metal grid flexible transparent electrode and the photovoltaic device.
The preparation method of the random metal grid flexible transparent electrode comprises the following steps:
1) providing a hard growth substrate, and preparing and forming a sacrificial layer on the hard growth substrate;
2) heating the sacrificial layer, and controlling the heating temperature and time to crack the sacrificial layer randomly to generate a gap;
3) forming a metal layer on the surface of the sacrificial layer and the hard growth substrate between the random cracking gaps by a PVD method;
4) etching to remove the sacrificial layer, removing the metal layer grown on the sacrificial layer, and reserving the metal layer grown on the hard growth substrate so as to obtain a random metal grid template formed on the hard growth substrate;
5) electroplating metal on the random metal grid template, and increasing the thickness to 700-900 nm to obtain a random metal grid;
6) preparing a compact and uniform flexible film on a hard growth substrate with a random metal grid by adopting a CVD (chemical vapor deposition) method;
7) the flexible film and the random metal grid are taken off from the hard growth substrate together, so that the flat surface originally contacted with the hard growth substrate is exposed and is used as the surface of the flattened ultrathin flexible electrode.
The invention relates to a preparation method of a flexible photovoltaic device of a random metal grid flexible transparent electrode, which comprises the following steps:
1) providing a hard growth substrate, and preparing and forming a sacrificial layer on the hard growth substrate;
2) heating the sacrificial layer, and controlling the heating temperature and time to crack the sacrificial layer randomly to generate a gap;
3) forming a metal layer on the surface of the sacrificial layer and the hard growth substrate between the random cracking gaps by a PVD method;
4) etching to remove the sacrificial layer, removing the metal layer grown on the sacrificial layer, and reserving the metal layer grown on the hard growth substrate so as to obtain a random metal grid template formed on the hard growth substrate;
5) electroplating metal on the random metal grid template, and increasing the thickness to 700-900 nm to obtain a random metal grid;
6) preparing a compact and uniform flexible film on a hard growth substrate with a random metal grid by adopting a CVD (chemical vapor deposition) method;
7) the flexible film and the random metal grid are all uncovered from the hard growth substrate, so that the flat surface originally in contact with the hard growth substrate is exposed and serves as the surface of the flattened ultrathin flexible electrode;
8) adhering the surface of the flexible film without the random metal grid to the surface of the hard preparation substrate;
9) sequentially growing an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode on the surface of the flattened ultrathin flexible electrode; or a hole transmission layer, a perovskite light absorption layer, an electron transmission layer and a metal electrode are sequentially grown on the random metal grid flexible transparent electrode;
10) and removing the hard preparation substrate to prepare the flexible photovoltaic device with the formal structure or the trans-structure.
In the step 1), the hard growth substrate adopts a glass substrate, a quartz substrate or a silicon substrate; the sacrificial layer is made of metal oxide; the metal oxide is titanium oxide, aluminum oxide or zinc oxide.
In the step 2), the time for heating the sacrificial layer is 25-35 minutes; the temperature is 280-320 ℃.
In the step 3), the PVD method adopts thermal evaporation or magnetron sputtering. The metal layer is made of metal which does not react with the perovskite material, and is made of one or more of gold (Au), silver (Ag), aluminum (Al), nickel (Ni) and titanium (Ti); the thickness is 30 to 50 nm.
In step 4), the sacrificial layer of metal oxide is removed by an acid or alkali reaction.
In step 5), due to the characteristic that the electroplating process only deposits metal on the conductive position, the electroplated metal completely engraves the metal pattern in the step.
The electroplating process has the advantages of low cost, high deposition speed and accurate control of patterning through the conductive region, and the scheme of implementing the PVD thin-layer metal-electroplating thick-layer metal step by step is lower in cost than that of directly PVD thick-layer metal.
In step 6), the thickness of the flexible film is less than 5 μm, and the material is Parylene, which is Parylene-C (poly 2-chloro-p-xylene), Parylene-D (poly 2, 5-dichloro-p-xylene), Parylene-N (Parylene), Parylene VT4 ( poly 2,3,5, 6-tetrafluoro-p-xylene), Parylene AF4 ( poly 1,1 ', 4, 4' -tetrafluoro-p-xylene) or Parylene AF8 ( poly 1,1 ', 2,3,4, 4', 5, 6-octafluoro-p-xylene), and the thickness is less than 5 μm.
In step 8), the hard preparation base adopts a glass substrate, a quartz substrate or a silicon substrate.
The invention has the advantages that:
the invention effectively solves the problems of metal grid moire and surface roughness by the preparation based on random metal grid and the transfer printing planarization technology of Parylene; the random metal grid is embedded into the flexible film, so that the thickness of the random metal grid is not limited any more, and the transparency can be ensured and the extremely high conductivity can be realized; meanwhile, the invention can realize an ultrathin (<5 μm) ultra-light perovskite photovoltaic device with ultra-high energy-to-mass ratio based on the transparent electrode.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a random metal mesh flexible transparent electrode according to the present invention, wherein (a) is a cross-sectional view of a sacrificial layer after random cracking, (b) is a cross-sectional view of a metal layer formed on a hard growth substrate between a surface of the sacrificial layer and gaps of the random cracking, and (c) is a cross-sectional view of a random metal mesh template on the hard growth substrate;
FIG. 2 is a microscope image of a random metal mesh obtained according to one embodiment of the method for fabricating a random metal mesh flexible transparent electrode according to the present invention;
fig. 3 is a cross-sectional view of a photovoltaic device prepared from a random metal mesh flexible transparent electrode according to the present invention.
Detailed Description
The invention will be further elucidated by means of specific embodiments in the following with reference to the drawing.
As shown in fig. 1, the random metal mesh ultrathin flexible transparent electrode of the present embodiment includes: preparing and forming a sacrificial layer 02 on a hard growth substrate 01; heating the sacrificial layer 02, and controlling the heating temperature and time to crack the sacrificial layer randomly; forming a metal layer 03 on the surface of the sacrificial layer and the hard growth substrate between the random cracking gaps by a PVD method; etching to remove the sacrificial layer, removing the metal layer covered on the sacrificial layer together, and reserving the metal layer covered on the hard growth substrate so as to obtain a random metal grid template 04 on the hard growth substrate; electroplating metal on the random metal grid template, and increasing the thickness to 800nm to obtain a random metal grid as shown in FIG. 2; preparing a compact and uniform flexible film on a hard growth substrate with a random metal grid by adopting a CVD (chemical vapor deposition) method; the flexible film and the random metal grid are taken off from the hard growth substrate together, so that the flat surface originally contacted with the hard growth substrate is exposed and is used as the surface of the flattened ultrathin flexible electrode.
As shown in fig. 3, the photovoltaic device of the random metal grid flexible transparent electrode of the present embodiment includes: the flexible thin film comprises a flexible thin film 1, a random metal grid 2, a first transmission layer 3, a perovskite light absorption layer 4, a second transmission layer 5 and a metal electrode 6; in the formal structure, the first transport layer 3 is an electron transport layer, and the second transport layer 5 is a hole transport layer; in the trans structure, the first transport layer 3 is a hole transport layer, and the second transport layer 5 is an electron transport layer.
The perovskite light absorption layer is made of organic and inorganic perovskite materials.
Example one
The embodiment is used for preparing a flexible photovoltaic device with a formal structure, and the preparation method of the flexible photovoltaic device with the random metal grid flexible transparent electrode comprises the following steps:
1) immersing a glass substrate into a detergent for ultrasonic cleaning, rinsing the detergent by using deionized water, sequentially immersing the glass substrate into the deionized water, acetone and isopropanol for ultrasonic cleaning to obtain a hard growth substrate, and depositing ZnO on the hard growth substrate to form a sacrificial layer;
2) heating the sacrificial layer at 300 ℃ for 30 minutes to randomly crack the sacrificial layer, as shown in fig. 1 (a);
3) depositing Ni on the surface of the sacrificial layer by a PVD method, wherein the thickness is 40nm, and forming a metal layer on the surface of the sacrificial layer and the hard growth substrate between the gaps of the random cracks, as shown in figure 1 (b);
4) etching to remove the sacrificial layer, removing the metal layer grown on the sacrificial layer, and retaining the metal layer grown on the hard growth substrate, thereby obtaining a random metal grid template on the hard growth substrate, as shown in fig. 1 (c);
5) electroplating metal Ni on the random metal grid template, and increasing the thickness to 800nm to obtain a random metal grid as shown in FIG. 2;
6) depositing Parylene-C on a hard growth substrate with a random metal grid by adopting a CVD method, wherein the thickness of the Parylene-C is 3 mu m, and preparing a compact and uniform flexible film;
7) the flexible film and the random metal grid are taken off from the hard growth substrate together, so that the flat surface originally contacted with the hard growth substrate is exposed and is used as the surface of the flattened ultrathin flexible electrode;
8) adhering the surface of the flexible film without the random metal grid to a hard glass preparation substrate;
9) SnO (SnO) diluted by water in volume ratio of 1:2 is spin-coated on the surface of a Parylene/Ni random metal grid flexible transparent electrode2Carrying out spin coating on the aqueous dispersion at the rotating speed of 4000 revolutions per minute for 30 seconds, keeping the temperature at 150 ℃ for 30 minutes after the spin coating is finished, transferring the aqueous dispersion into an ultraviolet-ozone cleaning machine for cleaning for 20 minutes, transferring the aqueous dispersion into a glove box, and naturally cooling the aqueous dispersion to room temperature to finish annealing to form an electron transport layer; mixing lead iodide (PbI)2) Dissolving the mixture in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), heating the DMSO and the DMF at a volume ratio of 1:9 at 70 ℃ to completely dissolve the mixture, then spin-coating the mixture on the electron transport layer prepared in the previous step at a spin-coating rotation speed of 2000 revolutions per minute for 30 seconds, keeping the spin-coating at 70 ℃ for 1 minute after the spin-coating is finished, and then naturally cooling the mixture to room temperature to finish annealing to form a perovskite light absorption layer; 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino]-9,9' -spirobifluorene (Spiro-OMeTAD) was dissolved in Chlorobenzene (CB) solvent at a concentration of 72.3mg/mL with vigorous stirring to completely dissolve it, and then 28.8. mu.L of 4-tert-butylpyridine (4-tert-butylpyridine) and 17.5. mu.L of lithium bistrifluoromethanesulfonylimide (Li-TFSI) in acetonitrile (concentration of 520mg/mL) were added to 1mL of the solution in this order, stirred uniformly, and then spin-coated on the perovskite layer prepared in the previous step at a spin-coating speed of 4000 revolutions per minute at the time of spin-coatingForming a hole transport layer within 30 seconds; transferring the metal film into a metal evaporation chamber, and preparing a gold (Au) electrode with the thickness of 80nm by using a vacuum thermal evaporation method and matching with a mask plate to form a metal electrode;
10) and removing the hard preparation substrate to prepare the flexible photovoltaic device with the formal structure.
Example two
The embodiment is used for preparing a flexible photovoltaic device with a trans-structure, and the preparation method of the flexible photovoltaic device with the random metal grid flexible transparent electrode comprises the following steps:
1) immersing a glass substrate into a detergent for ultrasonic cleaning, rinsing the detergent by using deionized water, sequentially immersing the glass substrate into the deionized water, acetone and isopropanol for ultrasonic cleaning to obtain a hard growth substrate, and depositing TiO on the hard growth substrate2Preparing and forming a sacrificial layer;
2) heating the sacrificial layer at 300 ℃ for 30 minutes to crack the sacrificial layer randomly;
3) depositing Ni on the surface of the sacrificial layer by a PVD method, wherein the thickness of the Ni is 40nm, and forming a metal layer on the surface of the sacrificial layer and the hard growth substrate between random cracking gaps;
4) etching to remove the sacrificial layer, removing the metal layer grown on the sacrificial layer, and reserving the metal layer grown on the hard growth substrate so as to obtain a random metal grid template on the hard growth substrate;
5) electroplating Ni on the random metal grid template, and increasing the thickness to 800nm to obtain a random metal grid;
6) depositing Parylene-C on a hard growth substrate with a random metal grid by adopting a CVD method, wherein the thickness of the Parylene-C is 3 mu m, and preparing a compact and uniform flexible film;
7) the flexible film and the random metal grid are taken off from the hard growth substrate together, so that the flat surface originally contacted with the hard growth substrate is exposed and is used as the surface of the flattened ultrathin flexible electrode;
8) adhering the surface of the flexible film without the random metal grid to the surface of the hard preparation substrate of the glass;
9) spin-coating a poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS) solution on the surface of the Parylene/Ni random metal grid flexible transparent electrode at 2000 rpm for 30 seconds, heating at 130 ℃ for 30 minutes after the spin-coating is finished, and naturally cooling to room temperature for annealing; dissolving poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine (PTAA) in Chlorobenzene (CB) with the concentration of 2mg/mL, spin-coating on a PEDOT (PSS) layer, wherein the spin-coating speed is 4000 rpm, the spin-coating time is 30 seconds, heating and keeping at the temperature of 150 ℃ for 20 minutes after the spin-coating is finished, naturally cooling to room temperature, and annealing to form a hole transport layer; weighing lead iodide (PbI) according to the required proportion2) Lead bromide (PbBr)2) Putting five powders of formamidine iodine (FAI), methylamine bromide (MABr) and cesium iodide (CsI) into a same reagent bottle, adding a mixed solvent of DMSO and DMF (volume ratio of the DMSO to the DMF is 1: 4), controlling the concentration of lead ions in the final precursor solution to be 1.41mmol/mL, placing the precursor solution on a heating table at 90 ℃ to be heated to be fully dissolved, then cooling to room temperature, spin-coating the solution on a hole transport layer in a two-step mode, wherein the spin-coating speed of the first step is 2000 rpm, the spin-coating time is 10 seconds, the spin-coating speed of the second step is 6000 rpm, the spin-coating time is 30 seconds, dropwise adding 100 microliters of an anti-solvent above a substrate 15 seconds before the spin-coating of the second step is finished, heating at 100 ℃ after the spin coating is finished, keeping for 60 minutes, and then naturally cooling and annealing to form a perovskite light absorption layer; mixing fullerene derivative PC61Dissolving BM in a CB solvent, wherein the concentration of BM is 20mg/mL, stirring for 2 hours on a hot bench at 60 ℃, and spin-coating on the prepared perovskite light absorption layer at the spin-coating speed of 1000 rpm for 30 seconds to obtain an electron transmission layer; spin-coating isopropanol saturated solution of Bathocuproine (BCP) on the electron transmission layer to form a buffer layer, wherein the spin-coating speed is 1000 rpm, the spin-coating time is 30 seconds, then transferring the buffer layer into a metal evaporation cabin, and preparing copper with the thickness of 80nm by using a vacuum thermal evaporation method and matching with a mask plate to obtain a metal electrode;
10) and removing the hard preparation substrate to prepare the trans-structure flexible photovoltaic device.
Finally, it is noted that the disclosed embodiments are intended to aid in further understanding of the invention, but those skilled in the art will appreciate that: various substitutions and modifications are possible without departing from the spirit and scope of the invention and the appended claims. Therefore, the invention should not be limited to the embodiments disclosed, but the scope of the invention is defined by the appended claims.

Claims (6)

1. A preparation method of a random metal grid ultrathin flexible transparent electrode is characterized in that a sacrificial layer is prepared and formed on a hard growth substrate; heating the sacrificial layer, wherein the sacrificial layer is made of metal oxide, and the heating temperature and time are controlled to crack the sacrificial layer randomly to generate gaps; forming a metal layer on the surface of the sacrificial layer and the hard growth substrate between the random cracking gaps by a physical vapor deposition method, wherein the metal layer is made of titanium; etching to remove the sacrificial layer, removing the metal layer grown on the sacrificial layer, and reserving the metal layer grown on the hard growth substrate so as to obtain a random metal grid template formed on the hard growth substrate; electroplating metal on the random metal grid template, and increasing the thickness to 700-900 nm to obtain a random metal grid; preparing a compact and uniform flexible film on a hard growth substrate with a random metal grid by adopting a chemical vapor deposition method, wherein the flexible film adopts poly-2-chloro-p-xylene, poly-2, 5-dichloro-p-xylene, parylene, poly-2, 3,5, 6-tetrafluoro-p-xylene, poly-1, 1 ', 4, 4' -tetrafluoro-p-xylene or poly-1, 1 ', 2,3,4, 4', 5, 6-octafluoro-p-xylene; the thickness of the flexible film is less than 5 microns; the flexible film and the random metal grid are taken off from the hard growth substrate together, so that the flat surface originally contacted with the hard growth substrate is exposed and is used as the surface of the flattened ultrathin flexible electrode.
2. The method for preparing the random metal grid ultrathin flexible transparent electrode as claimed in claim 1, wherein a glass substrate, a quartz substrate or a silicon substrate is adopted as the hard growth substrate.
3. A preparation method of a flexible photovoltaic device is characterized in that a sacrificial layer is prepared and formed on a hard growth substrate, and the sacrificial layer is made of metal oxide; heating the sacrificial layer, and controlling the heating temperature and time to crack the sacrificial layer randomly to generate a gap; forming a metal layer on the surface of the sacrificial layer and the hard growth substrate between the random cracking gaps by a physical vapor deposition method, wherein the metal layer is made of titanium; etching to remove the sacrificial layer, removing the metal layer grown on the sacrificial layer, and reserving the metal layer grown on the hard growth substrate so as to obtain a random metal grid template formed on the hard growth substrate; electroplating metal on the random metal grid template, and increasing the thickness to 700-900 nm to obtain a random metal grid; preparing a compact and uniform flexible film on a hard growth substrate with a random metal grid by adopting a chemical vapor deposition method, wherein the flexible film adopts poly-2-chloro-p-xylene, poly-2, 5-dichloro-p-xylene, poly-2, 3,5, 6-tetrafluoro-p-xylene, poly-1, 1 ', 4, 4' -tetrafluoro-p-xylene or poly-1, 1 ', 2,3,4, 4', 5, 6-octafluoro-p-xylene; the thickness of the flexible film is less than 5 microns; the flexible film and the random metal grid are taken off from the hard growth substrate together, so that the flat surface originally contacted with the hard growth substrate is exposed and is used as the surface of the flattened ultrathin flexible electrode; adhering the surface of the flexible film without the random metal grid to the surface of the hard preparation substrate; growing an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode on the surface of the flattened ultrathin flexible electrode in sequence; or, a hole transport layer, a perovskite light absorption layer, an electron transport layer and a metal electrode are sequentially grown on the random metal grid flexible transparent electrode.
4. A method for preparing a flexible photovoltaic device according to claim 3, wherein the hard preparation base is a glass substrate, a quartz substrate or a silicon substrate.
5. The random metal grid ultrathin flexible transparent electrode obtained by the preparation method of claim 1.
6. A flexible photovoltaic device obtained by the preparation method of claim 3.
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