CN113745409A - Preparation method of high-quality high-stability perovskite active layer and solar cell - Google Patents

Preparation method of high-quality high-stability perovskite active layer and solar cell Download PDF

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CN113745409A
CN113745409A CN202110870607.5A CN202110870607A CN113745409A CN 113745409 A CN113745409 A CN 113745409A CN 202110870607 A CN202110870607 A CN 202110870607A CN 113745409 A CN113745409 A CN 113745409A
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perovskite
active layer
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余学功
杭鹏杰
谢江生
杨德仁
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Zhejiang University ZJU
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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Abstract

The invention discloses a preparation method of a high-quality high-stability perovskite active layer, which is characterized in that perovskite single crystals are subjected to secondary re-dissolution, then the perovskite active layer is prepared by a vacuum spin coating, anti-solvent spin coating or blade coating method, so that the problems of slightly wide band gap and weakened bond energy of perovskite caused by component deviation and residual stress of a traditional polycrystalline perovskite film are solved, the performance and the stability of a perovskite solar cell are greatly improved, and meanwhile, the current of the perovskite solar cell prepared by the method is remarkably broken through under the same component. The invention also provides a preparation method of the solar cell based on the single crystal re-dissolved perovskite active layer with adjustable band gap, and the related device structure comprises transparent conductive glass, an electron transport layer, the perovskite active layer, a hole transport layer and a metal electrode layer from bottom to top.

Description

Preparation method of high-quality high-stability perovskite active layer and solar cell
Technical Field
The invention belongs to the field of perovskite photovoltaics, and particularly relates to a method for preparing a band gap adjustable high-efficiency high-stability perovskite solar cell.
Background
Through rapid development in recent years, the efficiency of organic-inorganic metal halide perovskite solar cells with narrow band gaps (< 1.65eV) reaches over 25 percent and approaches the limit efficiency. The highest efficiency reported to date is 25.5%, and the theoretical band gap of the perovskite used for the device is 1.45 eV. Although the open voltage of the device reaches more than 1.2V and is close to the limit, the current of the device is only close to 25.5mA/cm because the perovskite thin film prepared by the traditional method has a plurality of defects and the band gap is larger than the theoretical band gap due to internal residual stress2Far below its Schottky limit (approaching 30 mA/cm)2). To further improve the efficiency of the solar cell, it is increasingly important to reduce the band gap of the perovskite with the same composition to break through the current. However, at present, only perovskite single crystals have a large band gap close to the ideal band gap, but the preparation of single crystal perovskite thin films is very difficult, so that the preparation of polycrystalline perovskite films with the properties similar to that of single crystal perovskites is of great significance.
At present, in the device structure of the traditional perovskite solar cell, perovskite (ABX) is used3) AX and BX are mostly used as precursor solution2The powder is mixed and then added with a solvent, and a device prepared by using the solution is often not efficient under the condition of no other treatment means; by adopting interface passivation, the open voltage of the battery can be improved, so that the overall efficiency is higher, but the current of the device is still lower, and the stability of the device still has a larger improvement space. Due to AX and BX2The purity of the powder is low and the perovskite phase is not necessarily formed in strict 1: the crystallization is carried out at a molar ratio of 1, so that the prepared polycrystalline perovskite film has more defects, and the existence of residual stress causes elongation of chemical bonds and poor lattice stability, thereby causing poor device stability. Therefore, it is of great significance to improve the intrinsic stability of perovskites.
Disclosure of Invention
The invention aims to disclose a preparation method of a high-quality and high-stability perovskite active layer and a preparation method of a solar cell based on the perovskite active layer.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a high-quality high-stability perovskite layer comprises the following specific steps:
and re-dissolving the perovskite single crystal to obtain a perovskite precursor solution, and then preparing the perovskite active layer with adjustable band gap on the substrate by using the perovskite precursor solution.
Further, the precursor solution is prepared by MAPbI3，MAPbBr3，FAPbI3And CsPbI3One or more of the single crystals are dissolved in a DMF/DMSO mixed solvent with a volume ratio of 8:1 according to a molar ratio to form the single crystals, and the total molar concentration is 1.4-1.8 mol/L. The band gap of the perovskite active layer is 1.5-1.7 eV.
Further, in the perovskite precursor solution, MAPbI3、FAPbI3、MAPbBr3And CsPbI3The molar ratio of the single crystals is 0-1: 0-0.4: 0-0.1; prepared perovskite active layer CsxFAyMA1-x-yPbIzBr3-zThe thickness of (a) is 500-1000 nm.
Further, the method for preparing the perovskite active layer with the adjustable band gap comprises the following steps:
antisolvent spin coating: and spin-coating the perovskite precursor solution on a substrate, wherein the rotation speed of the first 5s is 1000rpm, and the rotation speed of the second 25s is 5000 rpm. 0.6-1.5ml of diethyl ether is dripped in the 15 th-20 th s, and then the sample is thermally treated at the temperature of 100 ℃ and 150 ℃ for 10-30min to prepare the perovskite active layer.
Or vacuum spin coating: and spin-coating the perovskite precursor solution on a substrate, wherein the rotation speed of the first 5s is 1000rpm, and the rotation speed of the second 25s is 5000 rpm. And after the spin coating is finished, immediately vacuumizing to below 30Pa and staying for 1-5min, and then performing heat treatment on the sample at the temperature of 100-150 ℃ for 10-30min to obtain the perovskite active layer.
Or knife coating method: the perovskite precursor solution is coated on the substrate in a blade mode, the blade coating speed is 20-40mm/s, and the slit distance is 100-200 mu m. And after the blade coating is finished, immediately vacuumizing to below 30Pa and staying for 1-5min, and then performing heat treatment on the sample at the temperature of 100-150 ℃ for 10-30min to obtain the perovskite active layer.
A preparation method of a high-efficiency high-stability perovskite layer solar cell comprises the following device structures from bottom to top: transparent conductive glass, an electron transport layer, a perovskite active layer, a hole transport layer and a metal electrode layer. The preparation method specifically comprises the following steps:
(1) preparing an electron transport layer on transparent conductive glass;
(2) the perovskite active layer is prepared on the electron transport layer by using the preparation method of the perovskite layer.
(3) And sequentially preparing a hole transport layer and a metal electrode layer on the perovskite active layer to obtain the high-efficiency and high-stability perovskite solar cell.
Furthermore, the transparent conductive glass (comprising a glass substrate and a transparent conductive electrode) is ITO or FTO transparent conductive glass, the square resistance of the transparent conductive glass is 5-15 omega, the light transmittance of the transparent conductive glass is 80-90%, the thickness of the transparent conductive glass is 1-3 mm, and the thickness of the transparent conductive electrode material is 150-300 nm.
Furthermore, the electron transport layer is tin dioxide or titanium dioxide inorganic metal oxide, and the thickness is 30-100 nm.
Further, the tin dioxide is prepared by the following method:
and spin-coating 1-5% of tin dichloride nano-crystalline aqueous solution on transparent conductive glass at the rotating speed of 2000-5000 rpm for 30-60 s. And then, heating the sample for 30-90 min at 100-250 ℃ by using a heating table, and after cooling, placing the sample into ultraviolet ozone for treatment for 5-10 min.
Further, the hole transport layer is a Spiro-OMeTAD or a TBP and lithium salt doped Spiro-OMeTAD, and the thickness of the hole transport layer is 100-200 nm.
Furthermore, the metal electrode layer is made of gold or silver, and the thickness of the metal electrode layer is 80-140 nm.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to aBy prior use of AX and BX2Growing perovskite ABX3The perovskite precursor solution is prepared by single crystal and secondary dissolution, and due to the memory effect, the grown polycrystalline perovskite film has larger and compact crystal grains, good crystallinity and stability, and narrowed band gap which is closer to an ideal band gap, so that the prepared device has higher efficiency and increased stability by several orders of magnitude.
Drawings
FIG. 1 is a device structure of a perovskite solar cell in an embodiment of the invention;
FIG. 2 is a schematic scanning electron microscope of a perovskite thin film in example 1 of the present invention;
FIG. 3 is a schematic diagram showing the UV-VIS absorption spectrum of the perovskite thin film of example 1 of the present invention;
FIG. 4 is a graph showing the photostability test of the perovskite solar cell and the UV filter according to example 6 of the present invention;
FIG. 5 is a scanning electron microscope cross-sectional view of a perovskite solar cell in example 6 of the present invention;
FIG. 6 is a schematic scanning electron microscope of a perovskite thin film in example 8 of the present invention;
FIG. 7 is a total spectral light stability test chart of a perovskite solar cell in example 8 of the present invention;
Detailed Description
The invention introduces a preparation method of a high-quality high-stability perovskite active layer and a preparation method of a solar cell based on the perovskite active layer, a precursor solution is formed by dissolving perovskite single crystals to further prepare a stable perovskite thin film, the problems that the band gap of perovskite is slightly wide and the bond energy is weakened due to component deviation and residual stress of the traditional polycrystalline perovskite thin film are solved, and the perovskite band gap based on the method is adjustable and stable, and the prepared solar cell has high efficiency and good stability. The invention provides a basic approach for preparing the high-efficiency and high-stability unijunction perovskite solar cell, and has important significance for commercialization of the perovskite cell.
The present invention will be described in further detail with reference to specific examples, which are illustrative of the present invention but not limiting thereto.
Example 1
Preparing a perovskite active layer: MAPbI is added3The bulk single crystal is 620mg dissolved in DMF/DMSO mixed solvent with volume ratio of 8:1 and 0.7mL to prepare perovskite precursor solution. 40 μ L of the precursor solution was spin-coated on the electron transport layer at a rotation speed of 1000rpm for the first 5s and 5000rpm for the last 25s, 0.8ml of diethyl ether was added dropwise at the 20 th s, followed by heat treatment on a hot stage at 75 ℃ for 1 min. Then, the mixture is transferred to a hot bench with the temperature of 150 ℃ for heat treatment for 15min to obtain MAPbI3A layer;
FIG. 2 shows the MAPbI prepared3As can be seen from the scanning electron microscopic image of the perovskite thin film, the perovskite has large and dense crystal grains, no pores and uniformity. FIG. 3MAPbI3The ultraviolet and visible light absorption spectrum of the perovskite thin film shows that the band edge absorption cutoff wavelength is 795nm, which shows that the band gap of the perovskite is 1.55eV, which is more than that of the traditional MAPbI3The bandgap of the film is narrow (-1.6 eV).
Example 2
Preparing a perovskite active layer: to FAPBI3633mg of bulk single crystal is dissolved in DMF/DMSO mixed solvent with the volume ratio of 8:1 and 0.7mL to prepare perovskite precursor solution. 40 μ L of the precursor solution was spin-coated on the electron transport layer at a rotation speed of 1000rpm for the first 5s and 5000rpm for the last 25s, and 1.5ml of diethyl ether was added dropwise at 15s, followed by heat treatment on a hot stage at 75 ℃ for 1 min. Then, transferring to a 100 ℃ hot bench for heat treatment for 10min to obtain FAPBI3A layer; the FAPBI3The crystal grains of the perovskite layer are large and compact, have no holes and are uniform.
Example 3
Preparing a perovskite active layer: MAPbI is added3The bulk single crystal is 620mg dissolved in DMF/DMSO mixed solvent with volume ratio of 8:1 and 0.55mL to prepare perovskite precursor solution. Spin-coating 40 μ L of precursor solution on the electron transport layer at the first 5s rotation speed of 1000rpm, 5000rpm for the last 25s, 1ml of diethyl ether was added dropwise at 18s, followed by heat treatment for 1min on a 75 ℃ hot plate. Then, the mixture is transferred to a hot bench with the temperature of 100 ℃ for heat treatment for 10min to obtain MAPbI3A layer; the MAPbI3The crystal grains of the perovskite layer are large and compact, have no holes and are uniform.
Example 4
Preparing a perovskite active layer: mixing CsPbI3721mg of bulk single crystal is dissolved in a DMF/DMSO mixed solvent with the volume ratio of 8:1 and 0.7mL to prepare a perovskite precursor solution. 40 mul of the precursor solution was spin coated on the electron transport layer at 5000rpm for 30 s. Then, the vacuum is applied to 30Pa, and the reaction is kept for 5 min. Then heat-treating on a hot bench at 100 ℃ for 30min to obtain CsPbI3A layer; the CsPbI3The crystal grains of the perovskite layer are large and compact, have no holes and are uniform.
Example 5
Preparing a perovskite active layer: mixing CsPbI3721mg of bulk single crystal is dissolved in a DMF/DMSO mixed solvent with the volume ratio of 8:1 and 0.7mL to prepare a perovskite precursor solution. 40. mu.L of the precursor solution was drawn down on the electron transport layer at a draw down speed of 40mm/s and a slit distance of 100. mu.m. Then, the vacuum is pumped to 24Pa, and the time is kept for 1 min. Then heat-treating on a hot bench at 100 ℃ for 30min to obtain CsPbI3A layer; the CsPbI3The crystal grains of the perovskite layer are large and compact, have no holes and are uniform.
Example 6
As shown in fig. 1, the device structure of the perovskite solar cell is from bottom to top: the ITO transparent conductive glass comprises a glass substrate and an ITO transparent conductive electrode, an electron transport layer, a perovskite active layer, a hole transport layer and a metal electrode layer.
The preparation method comprises the following steps:
firstly, cleaning ITO conductive glass. Selecting ITO conductive glass with the square resistance of 5-15 omega, the light transmittance of 85-90% and the thickness of 2mm, carrying out ultrasonic cleaning in deionized water, acetone, ethanol and isopropanol solutions for 6min in sequence, then blowing the ITO conductive glass with nitrogen for drying, and then treating for 15min by adopting an ultraviolet ozone cleaning machine;
two, revolveAnd coating an electron transport layer. Compounding SnO2A tin dioxide precursor solution with 1.5% mass fraction of nano-crystals (the grain size is 5-10nm in the embodiment). And (3) spin-coating 40 mu L of tin dioxide precursor solution on the ITO conductive glass at the rotation speed of 4000rpm for 30 s. Subsequently, the sample coated with the electron transport layer by the spin coating process is preheated at 150 ℃ for 30min by using a heating table to obtain dry and dense SnO2Cooling, and treating in ultraviolet ozone for 5 min;
thirdly, the perovskite active layer is spin-coated on the electron transport layer by using the method of the embodiment 1 to obtain MAPbI3A layer 1; preparation of conventional precursor solution (461mg of lead iodide and 159mg of MAI powder dissolved in DMF/DMSO mixed solvent at a volume ratio of 8:1 and 0.7 mL) MAPbI was prepared on the electron transport layer by the spin coating method of example 13A layer 2; perovskite precursor solution (630 mgMAPbI) dissolved by perovskite crystal powder is prepared3Powder dissolved in DMF/DMSO mixed solvent with volume ratio of 8:1 and 0.7 mL) prepared MAPbI on the electron transport layer by the spin coating method of example 13Layer 3.
Fourthly, spin coating a hole transport layer on the 3 perovskite layers. A mixed solution of spiro-OMeTAD was prepared by adding an acetonitrile solution containing 72.3mg of spiro-OMeTAD, 17.5. mu.L of lithium bisimide at a concentration of 520mg/mL and 28.8. mu.L of TBP to 1mL of chlorobenzene solvent. 40 μ L of the spiro-OMeTAD mixed solution was dropped on the surface of the perovskite active layer and spin-coated at 3000rpm for 30 s.
Fifthly, metal electrode layers are thermally evaporated. Adopting a thermal evaporation coating machine at-1.0 multiplied by 10-3And thermally evaporating 100nm of gold onto the hole transport layer under Pa vacuum to form a metal electrode layer. A perovskite solar cell 1, a perovskite solar cell 2, and a perovskite solar cell 3 were respectively fabricated.
The performance parameters of the perovskite solar cell 1, the perovskite solar cell 2 and the perovskite solar cell 3 obtained in the present example are shown in table 1, and it is known that the perovskite solar cell manufactured by the single crystal re-dissolving method of the present invention has higher energy conversion efficiency and less hysteresis. According to the continuous illumination stability test of the ultraviolet filter added in the figure 4, the efficiency is still kept above 80% after 500 hours of illumination, and the illumination stability of the battery is good. The invention greatly promotes the application and commercialization of the perovskite solar cell.
TABLE 1 Performance parameters of perovskite solar cells
Figure BDA0003188976570000051
Figure BDA0003188976570000061
Example 7
Firstly, cleaning ITO conductive glass.
Secondly, spin coating an electron transport layer. Compounding SnO2A tin dioxide precursor solution with 1% mass fraction of nano-crystals (the grain size is 5-10nm in the embodiment). And (3) spin-coating 40 mu L of tin dioxide precursor solution on the ITO conductive glass at the rotating speed of 3000rpm for 45 s. Subsequently, the sample coated with the electron transport layer by the spin coating process is preheated for 80min at 100 ℃ by using a heating table to obtain dry and dense SnO2Cooling, and then putting into ultraviolet ozone for treatment for 10 min;
third, in this embodiment, MAPbI is added331mg of single crystal, FAPBI3601mg of single crystal is dissolved in DMF/DMSO mixed solvent with the volume ratio of 8:1 and 0.59mL to prepare perovskite precursor solution. 40 mul of the precursor solution was spin coated on the electron transport layer at 5000rpm for 30 s. Then, the mixture was evacuated to 25Pa and left for 3 min. Then heat-treating on a hot stage at 150 deg.C for 15min to obtain a composition (FAPBI)3)0.95(MAPbI3)0.05The perovskite active layer of (1).
And fourthly, spin coating the hole transport layer. A mixed solution of spiro-OMeTAD was prepared by adding an acetonitrile solution containing 72.3mg of spiro-OMeTAD, 17.5. mu.L of lithium bisimide at a concentration of 520mg/mL and 28.8. mu.L of TBP to 1mL of chlorobenzene solvent. 40 μ L of the spiro-OMeTAD mixed solution was dropped on the surface of the perovskite active layer and spin-coated at 3000rpm for 35 s.
Fifthly, heat-evaporating metalAnd an electrode layer. Adopting a thermal evaporation coating machine at-1.0 multiplied by 10-3Under Pa vacuum, 80nm of gold was thermally evaporated onto the hole transport layer to form a metal electrode layer.
Fig. 5 is a scanning electron microscope cross-sectional view of the perovskite solar cell obtained by the preparation, and it is clear that the perovskite has good crystallinity, is dense, and has no pores. As shown in table 2, it is understood that the perovskite solar cell obtained in this example has high energy conversion efficiency and small hysteresis.
TABLE 2 Performance parameters of perovskite solar cells
Figure BDA0003188976570000062
Example 8
Firstly, cleaning ITO conductive glass.
Secondly, spin coating an electron transport layer. Compounding SnO2A tin dioxide precursor solution with the mass fraction of 3% of nano crystals (the grain size is 5-10nm in the embodiment). And (3) spin-coating 40 mu L of tin dioxide precursor solution on the ITO conductive glass at the rotating speed of 4500rpm for 30 s. Subsequently, the sample coated with the electron transport layer by the spin coating process is preheated at 200 ℃ for 30min by using a heating table to obtain dry and dense SnO2Cooling, and then putting into ultraviolet ozone for treatment for 7 min;
third, in this embodiment, CsPbI3The single crystal was 28.8mg, MAPbBr3The single crystal is 191.6mg, FAPBI3The single crystal of 354.5mg is dissolved in DMF/DMSO mixed solvent with the volume ratio of 8:1 and 0.58mL to prepare perovskite precursor solution. 40. mu.L of the precursor solution was drawn down on the electron transport layer at a draw down speed of 30mm/s and a slit distance of 150. mu.m. Then, the vacuum is applied to 30Pa, and the reaction is kept for 5 min. Then heat-treating on a hot bench at 150 deg.C for 15min to obtain perovskite component (CsPbI)3)0.04(FAPbI3)0.56(MAPbBr3)0.4And (3) a layer. FIG. 6 is a scanning electron microscope image of the perovskite thin film prepared at the temperature, and as can be seen from the image, the perovskite thin film prepared at the temperature has large crystal grains and clear grain boundaries。
And fourthly, spin coating the hole transport layer. A solution of 72.3mg of spirol-OMeTAD in 1mL of chlorobenzene was prepared. 40 μ L of spiro-OMeTAD solution was dropped on the surface of the perovskite active layer and spin-coated at 3000rpm for 35 s.
Fifthly, metal electrode layers are thermally evaporated. Adopting a thermal evaporation coating machine at-1.0 multiplied by 10-3And thermally evaporating 140nm of silver onto the hole transport layer under Pa vacuum to form a metal electrode layer.
The performance parameters of the perovskite solar cell obtained in this example are shown in table 3, and it is understood that the energy conversion efficiency of the cell is high and the hysteresis is small.
TABLE 3 Performance parameters of perovskite solar cells
Figure BDA0003188976570000071
As can be seen from fig. 7, the perovskite solar cell prepared at this temperature has good full spectrum (including ultraviolet) light stability, which is helpful for commercialization of the cell.
The above description is only a non-limiting embodiment of the present invention, and it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the inventive concept and without inventive step, and these changes and modifications are all within the scope of the present invention.

Claims (10)

1. A preparation method of a high-quality high-stability perovskite layer is characterized by comprising the following steps:
and re-dissolving the perovskite single crystal to obtain a perovskite precursor solution, and then preparing the perovskite active layer with adjustable band gap on the substrate by using the perovskite precursor solution.
2. The method of claim 1, wherein the precursor solution is prepared from MAPbI3，MAPbBr3，FAPbI3And CsPbI3Dissolving one or more of single crystals in DMF/DMSO mixed solvent at a volume ratio of 8:1 according to molar ratioThe total molar concentration is 1.4-1.8 mol/L. The band gap of the perovskite active layer is 1.5-1.7 eV.
3. The method of claim 1, wherein: in perovskite precursor solution, MAPbI3、FAPbI3、MAPbBr3And CsPbI3The molar ratio of the single crystals is 0-1: 0-0.4: 0-0.1; the thickness of the prepared perovskite active layer is 500-1000 nm.
4. The production method according to claim 1, wherein the method for producing the bandgap-tunable perovskite active layer is specifically:
antisolvent spin coating: and spin-coating the perovskite precursor solution on a substrate, wherein the rotation speed of the first 5s is 1000rpm, and the rotation speed of the second 25s is 5000 rpm. 0.6-1.5ml of diethyl ether is dripped in the 15 th-20 th s, and then the sample is thermally treated at the temperature of 100 ℃ and 150 ℃ for 10-30min to prepare the perovskite active layer.
Or vacuum spin coating: and spin-coating the perovskite precursor solution on a substrate, wherein the rotation speed of the first 5s is 1000rpm, and the rotation speed of the second 25s is 5000 rpm. And after the spin coating is finished, immediately vacuumizing to below 30Pa and staying for 1-5min, and then performing heat treatment on the sample at the temperature of 100-150 ℃ for 10-30min to obtain the perovskite active layer.
Or knife coating method: the perovskite precursor solution is coated on the substrate in a blade mode, the blade coating speed is 20-40mm/s, and the slit distance is 100-200 mu m. And after the blade coating is finished, immediately vacuumizing to below 30Pa and staying for 1-5min, and then performing heat treatment on the sample at the temperature of 100-150 ℃ for 10-30min to obtain the perovskite active layer.
5. The preparation method of the high-efficiency high-stability perovskite layer solar cell is characterized in that the device structure of the high-efficiency high-stability perovskite solar cell is as follows from bottom to top: transparent conductive glass, an electron transport layer, a perovskite active layer, a hole transport layer and a metal electrode layer. The preparation method specifically comprises the following steps:
(1) preparing an electron transport layer on transparent conductive glass;
(2) preparing a perovskite active layer on the electron transport layer by the preparation method according to any one of claims 1 to 4.
(3) And sequentially preparing a hole transport layer and a metal electrode layer on the perovskite active layer to obtain the high-efficiency and high-stability perovskite solar cell.
6. The method of claim 5, wherein: the transparent conductive glass (including the glass substrate and the transparent conductive electrode) is ITO or FTO transparent conductive glass, the square resistance of the transparent conductive glass is 5-15 omega, the light transmittance of the transparent conductive glass is 80-90%, the thickness of the transparent conductive glass is 1-3 mm, and the thickness of the transparent conductive electrode material is 150-300 nm.
7. The method of claim 5, wherein: the electron transmission layer is tin dioxide or titanium dioxide inorganic metal oxide, and the thickness is 30-100 nm.
8. The method of claim 7, wherein: the tin dioxide is prepared by the following method:
and spin-coating 1-5% of tin dichloride nano-crystalline aqueous solution on transparent conductive glass at the rotating speed of 2000-5000 rpm for 30-60 s. And then, heating the sample for 30-90 min at 100-250 ℃ by using a heating table, and after cooling, placing the sample into ultraviolet ozone for treatment for 5-10 min.
9. The method of claim 5, wherein: the hole transport layer is a Spiro-OMeTAD or a TBP and lithium salt doped Spiro-OMeTAD, and the thickness of the hole transport layer is 100-200 nm.
10. The method of claim 5, wherein: the metal electrode layer is made of gold or silver, and the thickness of the metal electrode layer is 80-140 nm.
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