CN108389971B - Large-area rutile phase SnO2Low-temperature preparation method and application of thin film - Google Patents
Large-area rutile phase SnO2Low-temperature preparation method and application of thin film Download PDFInfo
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Abstract
The invention relates to large-area rutile phase SnO2Low-temperature preparation method of thin film and application of thin film in perovskite solar cell. Large area SnO of the present invention2The film is prepared by putting clean FTO into a stannic chloride solution with the concentration of 0.02-0.7M, carrying out water bath at 70 ℃ for 2h, and then annealing at 70-200 ℃ for 1 h. The method has the advantages of simple operation, low cost, less by-products and little environmental pollution, and the prepared SnO2The film is uniform and compact, and has better crystallinity, permeability and conductivity. SnO prepared by the invention2Application of thin film to SnO2The electron transmission layer in the planar perovskite solar cell can obviously improve the short-circuit current of the cell, and the photoelectric conversion efficiency of the cell can reach more than 10 percent, so that the large-area rutile phase SnO prepared by the method disclosed by the invention2The film has good application prospect, and can be effectively applied to a planar perovskite solar cell.
Description
Technical Field
The invention belongs to the technical field of photoelectron materials and devices, and particularly relates to large-area rutile phase SnO2A low-temperature preparation method of the film and application of the film in perovskite solar cells.
Background
SnO2The film has the transmissivity of 80% in visible light and infrared ranges, has high band gap, high electron mobility and better stability, and is widely applied to perovskite solar cells. Despite these excellent properties and deep valence band values (believed to be effective in blocking photogenerated holes in the absorber), the tetragonal rutile structure of SnO2The film is generally synthesized by annealing at a temperature of more than 180-200 ℃, so that the application of the film in a flexible transparent substrate (such as PET or PEI, the bearing temperature is 100-150 ℃) is limited; meanwhile, due to the limitation of the synthesis process, it is difficult to form a uniform thin film with a large area, thereby preventing the application thereof to a large-area battery.
SnO reported in the literature of the prior art2The preparation method of the film mainly comprises the following steps: (1) sol-gel process by SnCl2·2H2SnO prepared by dissolving O in absolute ethyl alcohol2The organic sol is prepared by mixing the raw materials,SnO can be formed by spin coating a sol on a substrate and sintering at 450 deg.C2A dense electron transport layer; (2) low temperature Spin Coating (SC) of SnCl at room temperature4·5H2O preparation SnO2The electron transport layer is sintered at 180 ℃ in the air; (3) chemical Bath Deposition (CBD) method, placing the substrate in nontoxic aqueous solution of stannic chloride pentahydrate, and depositing for multiple times at 55 deg.C to increase thickness to obtain amorphous SnO2A film; (4) atomic deposition method (ALD) for preparing dense and uniform SnO by adopting plasma enhanced atomic deposition instrument2The deposition temperature of the film can be reduced to 100 ℃; (5) slurry spin coating method, SnO2Diluting the colloid precursor with water, spin-coating on a substrate, and baking on a hot plate at 150 ℃; (6) low temperature UV/ozone treatment in-situ synthesis, SnO synthesis of sol-gel using UV curing method2Depositing the precursor on a substrate, wherein the treatment temperature is 70 ℃; (7) microwave synthesis of nano crystal method, synthesizing high-dispersivity SnO in organic medium at 130 deg.C by microwave assistance2Nanoparticles, formation of homogeneous SnO at low temperatures using prepared nanoparticle ethanol dispersions2A film.
Prior art Synthesis of SnO2Different synthesis methods of the film have advantages and disadvantages, wherein the sol-gel method has the advantages that the process is simple, the synthesized film is compact and uniform, but the cycle is long and high-temperature annealing is required; the reported processing temperature of the slurry spin-coating method can only be reduced to 150 ℃; SnO synthesized by atomic deposition method2The film is more compact and uniform, but the cost is higher, and the limitation of the instrument and equipment is larger; the chemical bath deposition method grows at low temperature, does not need annealing treatment, has high transparency, and has the defects that the synthesized film is amorphous and the electron mobility is very low; the microwave synthesis method has the advantages that the synthesized film has larger crystal grains, the temperature is lower than 150 ℃, the film can be applied to a flexible transparent substrate, but the synthesis process is more complicated than other methods and is difficult to prepare on a large scale, so that the development of SnO which is simple to operate, can synthesize in a large area at a low temperature and has good crystallinity and excellent conductivity is urgently needed2A method of making a thin film.
Disclosure of Invention
For the backIn view of the problems identified in the art, it is an object of the present invention to provide a large-area rutile phase SnO2A low-temperature preparation method of the film and application of the film in perovskite solar cells. The invention solves the problem of large-area rutile phase SnO2The difficulty that the film can not be synthesized at low temperature is large-area SnO2The application of the film to a flexible substrate offers the possibility. In addition, the SnO prepared by the invention2The size distribution of the film is uniform, the crystallinity is good, the film can be effectively applied to a planar perovskite solar cell, and the film has a good application prospect.
In order to achieve the first object of the present invention, the inventors have conducted extensive experimental studies to develop a large-area rutile-phase SnO2The low-temperature preparation method of the film specifically comprises the following steps:
(1) cleaning a substrate: cleaning a transparent conductive substrate with a proper size by adopting a semiconductor process, and then drying the substrate for later use after ultraviolet ozone treatment;
(2) preparation of tin tetrachloride (SnCl)4) Aqueous solution: slowly dropwise adding anhydrous stannic chloride into deionized water, and uniformly stirring to obtain a stannic chloride aqueous solution, wherein the concentration of the stannic chloride aqueous solution is 0.02-0.7M;
(3) preparation of SnO2Film formation: putting the cleaned transparent conductive substrate in the step (1) into a culture dish, then adding the prepared stannic chloride aqueous solution in the step (2) into the culture dish, then putting the culture dish into a water bath kettle for water bath heating, controlling the water bath temperature to be 70 ℃ and the water bath time to be 2 hours, and depositing SnO on the surface of the transparent conductive substrate2Hydrosol; depositing SnO on the surface2Taking out the transparent conductive substrate of the hydrosol, cleaning the back of the substrate by using a cotton swab, sequentially cleaning by using an ultrasonic instrument, deionized water and absolute ethyl alcohol, and finally annealing under a low-temperature condition to form large-area rutile phase SnO on the substrate2And (3) annealing the film sample at the temperature of 70-200 ℃ for 1 h.
Further, in the above technical solution, the annealing temperature is preferably 70 ℃, 100 ℃ or 150 ℃.
Further, in the above technical solution, the transparent conductive substrate is preferably FTO.
It is another object of the present invention to provide a large-area rutile-phase SnO prepared as described above2Application of film, large area rutile phase SnO prepared by the invention2The film can be applied to SnO2Planar perovskite solar cells.
The above-mentioned SnO2The planar perovskite solar cell comprises a transparent conductive substrate, an electron transport layer, a perovskite active layer, a hole transport layer and a metal electrode, wherein the electron transport layer is SnO2The perovskite active layer is MAPbI3A film, wherein the hole transport layer is a Spiro-OMeTAD (2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group)]-9,9' -spirobifluorene) thin film, wherein said SnO2The film is the large-area rutile phase SnO prepared by the invention2A film.
Further, in the above technical solution, the thickness of the transparent conductive substrate is 380nm, the thickness of the electron transport layer is 20nm, the thickness of the perovskite active layer is 500nm, the thickness of the hole transport layer is 200nm, and the thickness of the metal electrode is 60 nm.
Further, in the above technical solution, the transparent conductive substrate is fluorine-doped tin oxide transparent conductive glass FTO, and the metal electrode is a gold electrode.
It is still another object of the present invention to provide the above-mentioned SnO2The preparation method of the planar perovskite solar cell specifically comprises the following steps:
(a) preparation of SnO on transparent conductive substrate2The film is used as an electron transport layer;
(b) preparation of MAPbI by spin coating on electron transport layer3The film is used as a perovskite active layer;
(c) preparing a Spiro-OMeTAD thin film as a hole transport layer by spin coating on the perovskite active layer;
(d) preparing a metal electrode on the hole transport layer by evaporation;
wherein, the SnO2The film is prepared by the methodLarge area rutile phase SnO2A film.
Further, the perovskite active layer in the above technical scheme has the following specific preparation process:
lead diiodide (PbI) is added according to the molar ratio of 1:12) Dissolving methylamine iodide (MAI) in mixed solvent of dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) at volume ratio of 4:1, stirring at 70 deg.C for 30min, and filtering to obtain MAPbI3A solution; coupling the MAPbI3Treating the solution with ultraviolet ozone for 15min, and spin-coating MAPbI at 3000 rpm3Uniformly spin-coating the solution on the electron transport layer, dripping appropriate amount of chlorobenzene which does not dissolve perovskite material in the process of substrate rotation, finally placing the spin-coated perovskite active layer in the air until the perovskite active layer becomes brown, and annealing at 100 ℃ for 10min to obtain MAPbI3A thin film perovskite active layer.
Further, the specific preparation process of the hole transport layer in the above technical scheme is as follows:
respectively dissolving 52mg of lithium salt and 30mg of cobalt salt in 76mg of acetonitrile to prepare an acetonitrile solution of the lithium salt and an acetonitrile solution of the cobalt salt; 72.3mg of Spiro-OMeTAD is dissolved in 1.1g of chlorobenzene, 28.8ul of TBP (4-tert-butylpyridine) is added, stirring is carried out for 15min, 17.5ul of a lithium salt acetonitrile solution and 29ul of a cobalt salt acetonitrile solution are added respectively, stirring is carried out for 30min, then filtration is carried out to obtain a Spiro-OMeTAD mixed solution, and the Spiro-OMeTAD mixed solution is coated on the perovskite active layer in a rotating mode at 4000 rpm to obtain the Spiro-OMeTAD thin film hole transport layer, wherein the rotating time is 20 s.
Compared with the prior art, the invention has the advantages and beneficial effects that:
(1) the invention preferably selects fluorine-doped tin oxide transparent conductive glass (FTO) as a substrate and uses anhydrous stannic chloride as a tin source to prepare SnCl4Heating the precursor aqueous solution in water bath to form SnO2Hydrosol, then a low-temperature annealing process is utilized to control the reaction temperature and time, and large-area uniform SnO is prepared on a transparent conductive substrate2A film. The method of the invention solves the problemsLarge area rutile phase SnO2The difficulty that the film can not be synthesized at low temperature is large-area SnO2The application of the film on a flexible substrate provides the possibility;
(2) SnO prepared by the invention2The particle size distribution in the film is uniform, the crystallinity, the permeability and the conductivity are all good, and SnO2The film is uniform and compact, and is SnO prepared by the traditional low-temperature method2Compared with a planar perovskite solar cell, the unmodified low-temperature SnO obtained by the invention2The short-circuit current of the planar perovskite solar cell is obviously improved, and the photoelectric conversion efficiency of a small area can reach more than 16%; meanwhile, the photoelectric conversion efficiency of the large-area perovskite solar cell can reach more than 10 percent, so that the large-area rutile phase SnO prepared by the method disclosed by the invention2The film has good application prospect, and can be effectively applied to a planar perovskite solar cell;
(3) the preparation method provided by the invention is simple to operate, low in experiment cost, few in experiment by-products, safe, reliable and small in environmental pollution.
Drawings
FIG. 1 is a SnO prepared according to example 2 of the present invention2A schematic structural diagram of a planar perovskite solar cell unit;
FIG. 2 is a SnO prepared according to example 1 of the present invention2Surface topography SEM test result chart of the film;
FIG. 3 shows SnO prepared in examples 2 to 4 of the present invention2XRD test result graph of the film;
FIG. 4 shows SnO prepared in examples 6 to 10 of the present invention2A light transmittance test result chart of the film;
FIG. 5 SnO prepared according to examples 6 to 10 of the present invention2And (3) a graph of the conductance test results of the film.
FIG. 6 shows a small-area SnO prepared in examples 12 to 17 of the present invention2J-V plot of planar perovskite solar cells;
FIG. 7 is a large-area SnO produced in example 18 of the present invention2J-V plot of planar perovskite solar cells;
FIG. 8 is a schematic representation of the practice of the present inventionLarge-area SnO prepared in example 182External quantum efficiency map of planar perovskite solar cells.
Detailed Description
The technical solution of the present invention is further explained in detail by the following specific examples and the accompanying drawings. The following embodiments are merely exemplary of the present invention, which is not intended to limit the present invention in any way, and those skilled in the art may modify the present invention in many ways by applying the teachings set forth above to equivalent embodiments with equivalent modifications. Any simple modification or equivalent changes made to the following embodiments according to the technical essence of the present invention, without departing from the technical spirit of the present invention, fall within the scope of the present invention.
Example 1
In this embodiment, a large-area rutile phase SnO2The low-temperature preparation method of the film specifically comprises the following steps:
(1) cleaning a substrate: selecting an FTO with a thickness of 1.1mm and a length and width of 2cm multiplied by 2cm in a square structure as a transparent conductive substrate, carrying out ultrasonic cleaning on the FTO by sequentially using a cleaning agent, deionized water, acetone and ethanol, carrying out ultrasonic treatment for 30min each time, treating each solvent for 1 time, cleaning impurities on an FTO substrate, carrying out ultraviolet ozone treatment for 15min, and finally blowing the FTO substrate in the air by using a blower for later use;
(2) measuring 0.02mol of anhydrous stannic chloride by using a rubber head dropper, dropwise and slowly adding the anhydrous stannic chloride into 1L of deionized water while stirring, and after dropwise adding is finished, continuously stirring for 1h to prepare a stannic chloride aqueous solution with the concentration of 0.02M;
(3) preparation of SnO2Film formation: putting the cleaned transparent conductive substrate in the step (1) into a culture dish, then adding the prepared stannic chloride aqueous solution in the step (2) into the culture dish, then putting the culture dish into a water bath kettle for water bath heating, controlling the water bath temperature to be 70 ℃ and the water bath time to be 2 hours, and depositing the surface of the transparent conductive substrate to form SnO2Hydrosol; depositing SnO on the surface2Taking out the transparent conductive substrate of the hydrosol, cleaning the back of the substrate by using a cotton swab, treating for 2-3 min by using an ultrasonic instrument, and sequentially using deionized water,Cleaning with absolute ethyl alcohol, and annealing on a heating table to form large-area rutile-phase SnO on the substrate2And (3) annealing the film sample at the annealing temperature of 70 ℃ for 1 h.
SnO prepared in this example was separately treated2The thin film samples were subjected to Scanning Electron Microscope (SEM) testing, which was conducted at 15 kV. SnO prepared in this example2SEM test results of the thin film samples are shown in FIG. 2, and it can be seen from FIG. 2 that SnO2The film is uniform and compact, and the particle size distribution in the film is uniform.
Example 2
In this embodiment, a large-area rutile phase SnO2The low temperature preparation of the film is the same as the preparation of example 1, except that: the annealing temperature in the step (3) was 100 ℃.
Example 3
In this embodiment, a large-area rutile phase SnO2The low temperature preparation of the film is the same as the preparation of example 1, except that: the annealing temperature in the step (3) was 150 ℃.
Example 4
In this embodiment, a large-area rutile phase SnO2The low temperature preparation of the film is the same as the preparation of example 1, except that: the annealing temperature in the step (3) was 200 ℃.
SnO prepared in examples 2 to 4 were each2The film samples were ground to powder and subjected to X-ray diffraction (XRD) analysis tests, in which: the instrument used for X-ray diffraction (XRD) analysis was D8Advance, the measurement conditions being 0.001 °/step scan. In FIG. 3, (a), (b) and (c) SnO prepared in example 2, example 3 and example 4, respectively2XRD test result chart of film sample. As can be seen from FIG. 3, SnO prepared in examples 2 to 42The film samples all had better crystallinity.
Example 5
In this embodiment, a large-area rutile phase SnO2The low temperature preparation of the film is the same as the preparation of example 1, except that: step four in step (2)The concentration of the aqueous tin chloride solution was 0.1M.
Example 6
In this embodiment, a large-area rutile phase SnO2The low temperature preparation of the film is the same as the preparation of example 1, except that: the concentration of the aqueous solution of tin tetrachloride in step (2) was 0.2M.
Example 7
In this embodiment, a large-area rutile phase SnO2The low temperature preparation of the film is the same as the preparation of example 1, except that: the concentration of the aqueous solution of tin tetrachloride in step (2) was 0.3M.
Example 8
In this embodiment, a large-area rutile phase SnO2The low temperature preparation of the film is the same as the preparation of example 1, except that: the concentration of the aqueous solution of tin tetrachloride in step (2) was 0.4M.
Example 9
In this embodiment, a large-area rutile phase SnO2The low temperature preparation of the film is the same as the preparation of example 1, except that: the concentration of the aqueous solution of tin tetrachloride in step (2) was 0.5M.
Example 10
In this embodiment, a large-area rutile phase SnO2The low temperature preparation of the film is the same as the preparation of example 1, except that: the concentration of the aqueous solution of tin tetrachloride in step (2) was 0.6M.
SnO prepared in examples 5 to 9 was treated with an ultraviolet-visible spectrophotometer2The film samples and clean FTO substrates were subjected to transmittance testing and the results are shown in fig. 4. As can be seen from FIG. 4, SnO prepared in examples 5 to 92The film samples all had better light transmission.
SnO prepared in examples 6 to 102The conductance of the film samples was measured and the results are shown in figure 5. As can be seen from FIG. 5, SnO prepared in examples 6 to 102The film samples all had better conductivity.
Example 11
Of the present embodimentSmall-area SnO2The planar perovskite solar cell comprises a transparent conductive substrate, an electron transport layer, a perovskite active layer, a hole transport layer and a metal electrode, wherein the electron transport layer is SnO2The perovskite active layer is MAPbI3A film, wherein the hole transport layer is a Spiro-OMeTAD (2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group)]-9,9' -spirobifluorene) thin film, wherein said SnO2The film is the large-area rutile phase SnO prepared by the invention2A film, wherein: the thickness of transparent conductive substrate be 380nm, the thickness of electron transport layer is 20nm, the thickness of perovskite active layer is 500nm, the thickness of hole transport layer is 200nm, the thickness of metal electrode is 60nm, transparent conductive substrate is fluorine-doped tin oxide transparent conductive glass FTO, the metal electrode be gold electrode, the electrode area is 6.0mm2。
The above-mentioned SnO2The preparation method of the planar perovskite solar cell specifically comprises the following steps:
(1) large-area rutile-phase SnO was prepared on a transparent conductive substrate in the same manner as in example 12Film is made
An electron transport layer;
(2) preparation of MAPbI by spin coating on electron transport layer3The thin film is used as a perovskite active layer
The specific preparation process comprises the following steps:
1.1064g of lead diiodide (PbI) was added in a molar ratio of 1:12) And 0.3816g methylamine iodide (MAI) in a mixed solvent of 1.5112g Dimethylformamide (DMF) and 0.44g dimethyl sulfoxide (DMSO) at a volume ratio of 4:1, stirring at 70 deg.C for 30min, and filtering to obtain MAPbI3A solution; coupling the MAPbI3Treating the solution with ultraviolet ozone for 15min, and spin-coating MAPbI at 3000 rpm3Uniformly spin-coating the solution on the electron transport layer for 40s, dripping appropriate amount of chlorobenzene which does not dissolve perovskite material in the process of rotating the substrate, and finally placing the spin-coated perovskite active layer in the air to be straightAnnealing at 100 deg.C for 10min to obtain MAPbI3A thin film perovskite active layer.
(3) A Spiro-OMeTAD thin film is prepared on a perovskite active layer in a spin coating mode and serves as a hole transport layer, and the specific preparation process of the hole transport layer is as follows:
respectively dissolving 52mg of lithium salt and 30mg of cobalt salt in 76mg of acetonitrile to prepare an acetonitrile solution of the lithium salt and an acetonitrile solution of the cobalt salt; 72.3mg of Spiro-OMeTAD is dissolved in 1.1g of chlorobenzene, 28.8ul of TBP (4-tert-butylpyridine) is added, stirring is carried out for 15min, 17.5ul of a lithium salt acetonitrile solution and 29ul of a cobalt salt acetonitrile solution are added respectively, stirring is carried out for 30min, then filtration is carried out to obtain a Spiro-OMeTAD mixed solution, and the Spiro-OMeTAD mixed solution is coated on the perovskite active layer in a rotating mode at 4000 rpm to obtain the Spiro-OMeTAD thin film hole transport layer, wherein the rotating time is 20 s.
(4) At 10-4Preparing a metal gold electrode on the hole transport layer by evaporation under the vacuum of Pa to obtain a metal gold electrode with the area of 0.06cm2Small area SnO2Planar perovskite solar cells.
Example 12
SnO of this example2The planar perovskite solar cell is the same as the cell structure and the preparation method of the embodiment 11, and the differences are only that: SnO adopted by electron transport layer in battery of the embodiment2The thin film was the large-area rutile-phase SnO prepared in example 5 above2A film.
Example 13
SnO of this example2The planar perovskite solar cell is the same as the cell structure and the preparation method of the embodiment 11, and the differences are only that: SnO adopted by electron transport layer in battery of the embodiment2The thin film was the large-area rutile-phase SnO prepared in example 6 above2A film.
Example 14
SnO of this example2The planar perovskite solar cell is the same as the cell structure and the preparation method of the embodiment 11, and the differences are only that: in the battery of this embodimentSnO adopted by electron transport layer2The thin film was the large-area rutile-phase SnO prepared in example 7 above2A film.
Example 15
SnO of this example2The planar perovskite solar cell is the same as the cell structure and the preparation method of the embodiment 11, and the differences are only that: SnO adopted by electron transport layer in battery of the embodiment2The thin film was the large-area rutile-phase SnO prepared in example 8 above2A film.
Example 16
SnO of this example2The planar perovskite solar cell is the same as the cell structure and the preparation method of the embodiment 11, and the differences are only that: SnO adopted by electron transport layer in battery of the embodiment2The thin film was the large-area rutile-phase SnO prepared in example 9 above2A film.
Example 17
SnO of this example2The planar perovskite solar cell is the same as the cell structure and the preparation method of the embodiment 11, and the differences are only that: SnO adopted by electron transport layer in battery of the embodiment2The thin film was the large-area rutile-phase SnO prepared in example 10 above2A film.
Example 18
Large-area SnO of the present example2The planar perovskite solar cell is the same as the cell structure and the preparation method of the embodiment 11, and the differences are only that: the electrode area in this example was 1cm2Large area SnO produced2The area of the planar perovskite solar cell is 1cm2。
The small-area SnO prepared in examples 12 to 172Planar perovskite solar cell and Large area SnO prepared in example 182And carrying out photoelectric performance test and external quantum efficiency test on the planar perovskite solar cell. The measurement of the current density (J-V) device was performed in a computer controlled Gishili 236 source measurement unit. The device characterization is carried out in an ambient atmosphere under illumination AM1.5G, at 100mW cm-2Xenon lamp based solar simulator (from Newport co., LTD.). The external quantum efficiency and Stenford research system model DSP phase-locked amplifier SR830 plus WDG3 monochrome suit and 500W xenon lamp measurement. The intensity of each wavelength of light is calibrated to a standard single crystal silicon photovoltaic cell.
Small-area SnO prepared in examples 12 to 172Planar perovskite solar cell and Large area SnO prepared in example 182The current density (J-V) test results of the planar perovskite solar cell are respectively shown in FIGS. 6 and 7; large area SnO prepared from example 182The results of the external quantum efficiency test of the planar perovskite solar cell are shown in fig. 8. As can be seen from the figure, the unmodified low-temperature SnO obtained by the invention2The short-circuit current of the planar perovskite solar cell is obviously improved, and the photoelectric conversion efficiency of a small area can reach more than 16%; meanwhile, the photoelectric conversion efficiency of the large-area perovskite solar cell can reach more than 10%.
Claims (10)
1. Large-area rutile phase SnO2The low-temperature preparation method of the film is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) cleaning a substrate: cleaning a transparent conductive substrate with a proper size by adopting a semiconductor process, and then drying the substrate for later use after ultraviolet ozone treatment;
(2) preparation of tin tetrachloride (SnCl)4) Aqueous solution: slowly dropwise adding anhydrous stannic chloride into deionized water, and uniformly stirring to obtain a stannic chloride aqueous solution, wherein the concentration of the stannic chloride aqueous solution is 0.02-0.7M;
(3) preparation of SnO2Film formation: putting the cleaned transparent conductive substrate in the step (1) into a culture dish, then adding the prepared stannic chloride aqueous solution in the step (2) into the culture dish, then putting the culture dish into a water bath kettle for water bath heating, controlling the water bath temperature to be 70 ℃ and the water bath time to be 2 hours, and depositing SnO on the surface of the transparent conductive substrate2Hydrosol; depositing SnO on the surface2Taking out the transparent conductive substrate of hydrosol, cleaning the back of the substrate with a cotton swab, and cleaningSequentially cleaning with an ultrasonic instrument, deionized water and absolute ethyl alcohol, and finally annealing at low temperature to form large-area rutile phase SnO on the substrate2And (3) annealing the film sample at the temperature of 70-150 ℃ for 1 h.
2. The large area rutile phase SnO of claim 12The low-temperature preparation method of the film is characterized by comprising the following steps: the annealing temperature is 70 ℃, 100 ℃ or 150 ℃.
3. The large area rutile phase SnO of claims 1 or 22The low-temperature preparation method of the film is characterized by comprising the following steps: the transparent conductive substrate is FTO.
4. A large area rutile phase SnO as claimed in claim 1 or 22Use of a film characterized by: said SnO2The film can be applied to SnO2Planar perovskite solar cells.
5. SnO (stannic oxide)2Planar perovskite solar cell, the battery includes transparent conductive substrate, electron transport layer, perovskite active layer, hole transport layer and metal electrode, its characterized in that: the electron transport layer is SnO2The perovskite active layer is MAPbI3A thin film, wherein the hole transport layer is a Spiro-OMeTAD thin film, and the SnO2The film is large-area rutile phase SnO prepared by the method of claim 1 or 22A film.
6. A SnO according to claim 52Planar perovskite solar cell, its characterized in that: the thickness of the transparent conductive substrate is 380nm, the thickness of the electron transport layer is 20nm, the thickness of the perovskite active layer is 500nm, the thickness of the hole transport layer is 200nm, and the thickness of the metal electrode is 60 nm.
7. According to claim 5SnO according to item 62Planar perovskite solar cell, its characterized in that: the transparent conductive substrate is fluorine-doped tin oxide transparent conductive glass FTO, and the metal electrode is a gold electrode.
8. The SnO of claim 52The preparation method of the planar perovskite solar cell is characterized by comprising the following steps: the method specifically comprises the following steps:
(a) preparation of SnO on transparent conductive substrate2The film is used as an electron transport layer;
(b) preparation of MAPbI by spin coating on electron transport layer3The film is used as a perovskite active layer;
(c) preparing a Spiro-OMeTAD thin film as a hole transport layer by spin coating on the perovskite active layer;
(d) and (4) evaporating and preparing a metal electrode on the hole transport layer.
9. A SnO according to claim 82The preparation method of the planar perovskite solar cell is characterized by comprising the following steps:
the perovskite active layer is prepared by the following specific preparation process:
lead diiodide (PbI) is added according to the molar ratio of 1:12) Dissolving methylamine iodide (MAI) in mixed solvent of dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) at volume ratio of 4:1, stirring at 70 deg.C for 30min, and filtering to obtain MAPbI3A solution; coupling the MAPbI3Treating the solution with ultraviolet ozone for 15min, and spin-coating MAPbI at 3000 rpm3Uniformly spin-coating the solution on the electron transport layer, dripping appropriate amount of chlorobenzene which does not dissolve perovskite material in the process of substrate rotation, finally placing the spin-coated perovskite active layer in the air until the perovskite active layer becomes brown, and annealing at 100 ℃ for 10min to obtain MAPbI3A thin film perovskite active layer.
10. A SnO according to claim 8 or 92The preparation method of the planar perovskite solar cell is characterized by comprising the following steps: the hole transport layer hasThe preparation process comprises the following steps:
respectively dissolving 52mg of lithium salt and 30mg of cobalt salt in 76mg of acetonitrile to prepare an acetonitrile solution of the lithium salt and an acetonitrile solution of the cobalt salt; 72.3mg of Spiro-OMeTAD is dissolved in 1.1g of chlorobenzene, 28.8ul of TBP (4-tert-butylpyridine) is added, stirring is carried out for 15min, 17.5ul of a lithium salt acetonitrile solution and 29ul of a cobalt salt acetonitrile solution are added respectively, stirring is carried out for 30min, then filtration is carried out to obtain a Spiro-OMeTAD mixed solution, and the Spiro-OMeTAD mixed solution is coated on the perovskite active layer in a rotating mode at 4000 rpm to obtain the Spiro-OMeTAD thin film hole transport layer, wherein the rotating time is 20 s.
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