CN108539026B - Preparation method of perovskite thin film with micron tube array structure - Google Patents
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
A preparation method of perovskite film with micron tube array structure comprises the steps of preparing conductive glass substrate; preparation of CH3NH3PbI3‑xClxA step of precursor solution; one-time spin coating of CH on conductive glass substrate3NH3PbI3‑xClxA step of precursor solution; spin coating a certain amount of deionized water; secondary spin coating of CH3NH3PbI3‑xClxA step of precursor solution; and (5) carrying out subsequent processing treatment. According to the preparation method of the perovskite thin film with the micron tube array structure, the perovskite thin film with the one-dimensional micron tube array structure, which is provided by the invention, is large in specific surface area, few in crystal boundary, low in defect density, high in carrier migration rate, good in conductivity, not easy to deliquesce in air, good in stability and strong in environmental adaptability is prepared through multiple-step unique process fine control and spin coating liquid selection.
Description
Technical Field
The invention relates to the technical field of light absorption materials of solar cells, in particular to a preparation method of a perovskite thin film with a microtube array structure.
Background
With the frequency of non-renewable energy sources such as coal, petroleum, natural gas and the like becoming urgent, the problems of energy depletion and serious environmental pollution increasingly become bottlenecks restricting the development of the economic society, and the development of renewable clean energy sources is a necessary trend of the social development. The inexhaustible clean energy serves as inexhaustible solar energy, and paves the way for the rapid development of solar cells. Solar cells are devices that convert light energy into electrical energy by a photoelectric or photochemical effect, also known as photovoltaic cells. As an emerging third-generation solar cell, namely a perovskite solar cell, the photoelectric conversion efficiency of the perovskite solar cell exceeds 22%, and the perovskite solar cell has a great commercial application prospect.
At present, the light absorption layer material used in the perovskite battery generally has the technical problems of poor stability in air, easy deliquescence, small specific surface area, limited carrier separation and transmission capability and poor conductivity. At present, the micro-arrangement structure of the existing perovskite thin film is a three-dimensional type, in the three-dimensional perovskite thin film structure, the diffusion length of a carrier is over 1 micron, and the separation of the carrier at the interface of a hole transmission layer and a perovskite light absorption layer is influenced by a longer transmission distance in the thin film structure, so that the possibility of carrier recombination is increased, and the transmission capability is poor. To improve and enhance carrier mobility, current scientific studies show that: compared with the existing three-dimensional perovskite light absorption layer structure, the low-dimensional perovskite light absorption layer structure has better performance, and can enable carriers to have faster transmission capacity in the transmission process.
The perovskite battery-based light absorption layer material has poor stability in air and is easy to deliquesce. In the prior art, some researchers add solvents such as toluene and chlorobenzene into a solution to adjust the forming process of the perovskite thin film in the preparation process of the perovskite thin film, so as to improve the stability of the perovskite thin film to water and oxygen. Although the stability of the perovskite film prepared by the method is improved to a certain extent in the air, the perovskite film has poor durability, and the anti-solvents such as toluene, chlorobenzene and the like used in the preparation process are toxic and pungent, have poor environmental protection property, are harmful to human health and are not beneficial to large-scale preparation of green batteries in the later period.
At present, no perovskite thin film which has good stability, difficult deliquescence, strong carrier transmission capability and prominent electrical conductivity exists in the prior art.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a perovskite thin film with a micron tube array structure, which prepares the perovskite thin film with a one-dimensional micron tube array structure, large specific surface area, few crystal boundaries, low defect density, high carrier migration rate, good conductivity, difficult deliquescence in the air, good stability and strong environmental adaptability through multi-step unique process fine control and spin coating liquid selection.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a perovskite thin film with a microtube array structure comprises the following steps:
taking a hard conductive glass substrate, carrying out ultrasonic cleaning on the surface of the hard conductive glass substrate by using acetone, alcohol and deionized water in sequence, then blowing the surface of the hard conductive glass substrate by using a nitrogen gun, and then putting the hard conductive glass substrate into an ozone machine for carrying out ozone treatment for 10-15 min to prepare a conductive glass substrate for later use;
step two, respectively taking CH according to the molar ratio of 1: 1-3: 13NH3I and PbCl2Mixing to prepare a mixed solute, adding an N, N-dimethylformamide solvent into the mixed solute according to the proportion of 0.1-0.3 mol/l between the mixed solute and the solvent, fully stirring and dissolving, placing the obtained mixed solution into an ultrasonic cleaner, and carrying out ultrasonic oscillation treatment for 8-14 h at the temperature of 40-60 ℃ to prepare CH3NH3PbI3-xClxPrecursor solution for later use;
step three, placing the conductive glass substrate prepared in the step one in a spin coater, controlling the temperature of the conductive glass substrate to be 60-70 ℃, controlling the rotating speed of the spin coater to be 2000-3000 r/min, and under the assistance of hot air, according to CH3NH3PbI3-xClxThe area of the precursor solution and the conductive glass substrate to be spin-coated is 30-50 mu l/cm2Measuring the CH prepared in the step two3NH3PbI3-xClxSpin-coating the precursor solution on the surface of a conductive glass substrate in a spin coater, then placing the conductive glass substrate in a vacuum drying oven, and annealing for 8-15 min at the temperature of 70-130 ℃ to prepare a primary spin-coated substrate for later use;
step four, adopting a liquid shifterMeasuring CH obtained in the third step3NH3PbI3-xClxDeionized water with the volume of 0.5-1.5% of the precursor solution is dripped on the surface of the one-time spin-coating substrate in the annealing atmosphere of 70-130 ℃ prepared in the third step, and before the dripped deionized water is not completely evaporated, the deionized water is dripped according to CH3NH3PbI3-xClxThe area of the precursor solution and the substrate to be spin-coated is 30-50 mu l/cm2Taking CH prepared in the second step3NH3PbI3-xClxAnd spin-coating the precursor solution on the surface of the primary spin-coating substrate to obtain a secondary spin-coating substrate, then annealing the obtained secondary spin-coating substrate at the temperature of 70-130 ℃ for 30-60 min until the liquid on the surface of the secondary spin-coating substrate is completely crystallized, cooling to room temperature to obtain the conductive substrate with the surface covered with the perovskite film with the micron tube array structure, and placing the conductive substrate in a culture dish for sealing and storage.
Preferably, in the step one, the conductive glass substrate is FTO transparent conductive glass.
Preferably, in the step one, the time of each ultrasonic cleaning is 10-15 min.
Preferably, in step three, the spin coating CH3NH3PbI3-xClxThe operation of the precursor solution needs to be completed within 20-30 s.
Preferably, in the third step, the temperature of the hot air assisted by the hot air is 60-70 ℃.
Preferably, in step four, the other CH is taken3NH3PbI3-xClxThe amount of precursor solution and CH spin-coated in step three3NH3PbI3-xClxThe amount of precursor solution was the same.
Preferably, in the fourth step, the amount of the deionized water dripped is CH taken in the third step3NH3PbI3-xClx1% of the volume of the precursor solution.
Preferably, in step four, the other CH is taken3NH3PbI3-xClxFront trunkWhen the liquid solution is used for spin coating on the surface of a primary spin coating substrate, the temperature of the primary spin coating substrate needs to be controlled to be 60-70 ℃, the rotating speed of a spin coater needs to be 2000-3000 r/min, and meanwhile, hot air assistance needs to be carried out, and the temperature of the hot air assistance is 60-70 ℃.
Has the advantages that:
1. the invention provides a preparation method of a perovskite thin film with a microtube array structure, which is used for solving the technical problem that the perovskite thin film is easy to react with water or oxygen in the air to decompose or oxidize the thin film. The method is characterized in that deionized water is dripped on the surface of the primary-annealed perovskite thin film through spin coating, and then the perovskite precursor solution is spin coated again before the deionized water is not completely evaporated, so that the uniform growth of crystal grains can be ensured, and the directionality of secondary-grown perovskite crystal grains can be controlled. The addition of deionized water in the intermediate step can enable the generated film to generate a dissolving and recrystallizing process, thereby realizing the modification of the film interface. Under the assistance of the dropwise added deionized water, the crystallization rate of the film is delayed to a certain degree, nucleation and growth of crystal grains are facilitated, and the film has a one-dimensional hollow micron tube array structure, so that the service life and the moving rate of carriers are effectively improved. More importantly: hydrogen bonds can be formed in the structure of the film dripped with the deionized water, so that the film is passivated and has stronger hydrophobicity, and the stability to the environment is improved. Meanwhile, in the process of multiple spin coating, deionized water is added, so that the orientation and uniformity of the micron tube array are obviously improved, and the uniform crystallization of the perovskite thin film is effectively controlled.
2. Compared with the perovskite thin film with other structures, the perovskite thin film with the micron tube array structure prepared by the invention has larger specific surface area and is more beneficial to the transmission of current carriers at the interface. In multiple spin coating operations, the doping of deionized water can play a good role in guiding the diameter and the directionality of the micron tube. The preparation method well prepares the perovskite thin film with few crystal boundaries, low defect density, larger specific surface area, high carrier migration rate and conductivity by a one-step solution method, and improves the conductivity of the thin film and the stability of the environment. The method has the advantages of simple operation, low cost, strong environmental friendliness, good repeatability and good stability, greatly improves the overall performance of the film, and lays a solid foundation for future industrial production.
Drawings
FIG. 1 is an SEM image of a perovskite thin film prepared in example 1;
FIG. 2 is an SEM image of a perovskite thin film prepared in example 2;
FIG. 3 is an SEM image of a perovskite thin film prepared in example 3;
FIG. 4 is an SEM image of a perovskite thin film prepared in comparative example 1;
FIG. 5 is an SEM image of a perovskite thin film prepared in comparative example 2;
FIG. 6 is a comparative XRD plot of perovskite thin films prepared in example 2 and comparative examples 1 and 2;
FIG. 7 is a PL comparison of perovskite thin films prepared in example 2 and comparative examples 1 and 2;
FIG. 8 is a graph comparing UV-vis of perovskite thin films prepared in example 2 and comparative examples 1 and 2;
Detailed Description
The technical solution of the present invention will be further explained and explained in detail with reference to the drawings and the specific embodiments.
The FTO transparent conductive glass used in the examples was purchased from south china technologies ltd; methyl amine iodide (CH)3NH3Powder I) analytically pure, lead chloride (PbCl)2) Analytically pure, edler (cheng du) technologies ltd; n, N-dimethylformamide (DMF is more than or equal to 99.5 percent) and becomes a chemical reagent factory of Polygala Kogyo.
A preparation method of a perovskite thin film with a microtube array structure comprises the following steps:
(1) ultrasonically cleaning the FTO transparent conductive glass for 10-15 min by using acetone, alcohol and deionized water in sequence each time, then blow-drying by using a nitrogen gun, and then placing the FTO glass substrate into an ozone machine for carrying out ozone treatment for 10-15 min;
(2)CH3NH3PbI3-xClxpreparing a precursor solution: will CH3NH3I and PbCl2Mixing and dissolving the components in a molar ratio of 1: 1-3: 1 in an N, N-dimethylformamide solvent, wherein the ratio of the solvent to the mixed solute is 0.1
About 0.3mol/l to produce CH3NH3PbI3-xClxOscillating the precursor solution in an ultrasonic cleaner for 8-14 h, and heating the ultrasonic cleaner to 40-60 ℃ to obtain the CH completely reacted3NH3PbI3-xClxA precursor solution.
(3) Deionized water doped CH3NH3PbI3-xClxPreparing a film: putting a conductive glass substrate into a spin coater, controlling the rotating speed of the spin coater to be 2000-3000 r/min, spin-coating for 20-30 s, heating the conductive glass substrate to 60-70 ℃, and spin-coating CH on the conductive glass substrate under the condition of utilizing 60-70 ℃ hot air for assistance3NH3PbI3-xClxThe hot air is used in the spin coating process of the precursor solution to accelerate the volatilization of the solvent in the precursor solution so that the spin coating solution is quickly crystallized to form the perovskite film, and CH is spin-coated3NH3PbI3-xClxThe amount of the precursor solution is 30-50 mul/cm2And then transferring the mixture into a vacuum drying oven at the temperature of 70-130 ℃ for heating, and carrying out annealing treatment for 8-15 min. Immediately dripping 0.5-1.5% (i.e. 0.25-1.5 μ l/cm) of the volume of the precursor solution on the surface of the annealed film by using a liquid transfer device2) The conductive glass substrate is still in an annealing atmosphere at 70-130 ℃ in the dripping and coating process, and a layer of CH is coated in a spinning mode before the deionized water is not completely evaporated3NH3PbI3-xClxThe amount of the precursor solution, the spin coating solution and the first spin coating are the same, the spin coating mode and the operating condition parameters in the spin coating process are also the same, and then the spin coating is carried out
And annealing for 30-60 min, cooling to room temperature after the precursor solution is completely crystallized, transferring the substrate into a culture dish, sealing and storing to prevent the substrate from being oxidized and decomposed in the air, and thus obtaining the finished product of the conductive substrate with the surface covered with the perovskite thin film with the micron tube array structure.
According to the invention, a certain volume fraction of the green solvent deionized water is added to form hydrogen bonds in the film, so that the film has stronger hydrophobicity, the stability in air is improved, and the film is not easy to be oxidized and deliquesced, and further the passivation effect is achieved, the perovskite film with the one-dimensional microtube array structure is successfully prepared, compared with other structures, the perovskite film with the microtube array structure has the advantages of larger specific surface area, fewer crystal boundaries, low defect density, high carrier migration rate and conductivity, and the stability of the film to the environment is improved.
Example 1:
a preparation method of a perovskite thin film with a microtube array structure comprises the following steps:
(1) cleaning and ozone treatment of FTO glass: cleaning FTO transparent conductive glass with a detergent, then respectively ultrasonically cleaning the FTO transparent conductive glass with acetone, deionized water, alcohol and deionized water for 10min in sequence, then blow-drying the FTO transparent conductive glass with a nitrogen gun, and then placing an FTO substrate into an ozone machine for ozone treatment for 15min to prepare a conductive glass substrate for later use;
(2)CH3NH3PbI3-xClxpreparing a precursor solution: will CH3NH3I and PbCl2Mixing and dissolving in N, N-dimethylformamide solvent according to the molar ratio of 1:1 to obtain CH3NH3PbI3-xClxOscillating the precursor solution in an ultrasonic cleaner for 8h, heating the ultrasonic cleaner to 60 ℃ to prepare CH3NH3PbI3-xClxPrecursor solution for later use;
(3) deionized water doped CH3NH3PbI3-xClxPreparing a film: placing the conductive glass substrate prepared in the step one in a spin coater, controlling the rotating speed to be 3000r/min, controlling the spin coating time to be 20s, heating the conductive glass substrate to 70 ℃, and spin-coating CH on the substrate by utilizing hot air assistance3NH3PbI3-xClxPrecursor solution, the amount of the spin-coating precursor solution is 50 mu l/cm2Then transferring the mixture into a vacuum drying oven to heat to 70 ℃, and carrying out annealing treatment for 15 min. Using a pipette to drip 0.5% (i.e. 0.25. mu.l/cm) of the volume of the precursor solution on the surface of the annealed film2) And (3) the substrate is still in an annealing atmosphere at 70 ℃ in the dripping coating process, a layer of precursor solution is spin-coated before the deionized water is not completely evaporated, the amount of the spin-coated solution is the same as that of the first spin-coating, the annealing time is 30min, after the precursor solution is completely crystallized, the substrate is cooled to room temperature, and the substrate is transferred into a culture dish to be sealed and stored to prevent the substrate from being oxidized and decomposed in the air, so that the conductive substrate with the surface covered with the perovskite film with the micron tube array structure is obtained.
Example 2:
a preparation method of a perovskite thin film with a microtube array structure comprises the following steps:
(1) cleaning and ozone treatment of FTO glass: cleaning FTO transparent conductive glass with a detergent, then respectively ultrasonically cleaning the FTO transparent conductive glass with acetone, deionized water, alcohol and deionized water for 12min in sequence, then blow-drying the FTO transparent conductive glass with a nitrogen gun, and then placing an FTO substrate into an ozone machine for ozone treatment for 14min to prepare a conductive glass substrate for later use;
(2)CH3NH3PbI3-xClxpreparing a precursor solution: will CH3NH3I and PbCl2Mixing and dissolving in N, N-dimethylformamide solvent according to the molar ratio of 2:1 to obtain CH3NH3PbI3-xClxOscillating the precursor solution in an ultrasonic cleaner for 10h, heating the ultrasonic cleaner to 50 ℃ to prepare CH3NH3PbI3-xClxPrecursor solution for later use;
(3) deionized water doped CH3NH3PbI3-xClxPreparing a film: placing the conductive glass substrate prepared in the step one in a spin coater, controlling the rotating speed to be 2500r/min, controlling the spin coating time to be 25s, heating the conductive glass substrate to 65 ℃, and spin-coating CH on the substrate by utilizing hot air assistance3NH3PbI3-xClxPrecursor solution, the amount of the spin-coating precursor solution is 40 mul/cm2Then transferring the mixture into a vacuum drying oven to heat to 100 ℃, and carrying out annealing treatment for 10 min. And (2) dropwise coating deionized water accounting for 1% of the volume of the precursor solution on the surface of the annealed film by using a liquid transfer device, wherein the substrate is still in an annealing atmosphere at 100 ℃ in the dropwise coating process, before the deionized water is not completely evaporated, a layer of precursor solution is further spin-coated, the amount of the spin-coated solution is the same as that of the first spin-coating, the annealing time is 50min, after the precursor solution is completely crystallized, the substrate is cooled to room temperature, and the substrate is transferred into a culture dish to be stored in a sealed manner to prevent the substrate from being oxidized and decomposed in the air, so that the conductive substrate with the surface covered with the perovskite film.
Example 3:
a preparation method of a perovskite thin film with a microtube array structure comprises the following steps:
(1) cleaning and ozone treatment of FTO glass: cleaning FTO transparent conductive glass with a detergent, then respectively ultrasonically cleaning the FTO transparent conductive glass with acetone, deionized water, alcohol and deionized water for 15min in sequence, then blow-drying the FTO transparent conductive glass with a nitrogen gun, and then placing an FTO substrate into an ozone machine for ozone treatment for 10min to prepare a conductive glass substrate for later use;
(2)CH3NH3PbI3-xClxpreparing a precursor solution: will CH3NH3I and PbCl2Mixing and dissolving in N, N-dimethylformamide solvent according to the molar ratio of 3:1 to obtain CH3NH3PbI3-xClxOscillating the precursor solution in an ultrasonic cleaner for 14h, heating the ultrasonic cleaner to 40 ℃ to prepare CH3NH3PbI3-xClxPrecursor solution for later use;
(3) deionized water doped CH3NH3PbI3-xClxPreparing a film: placing the conductive glass substrate prepared in the step one in a spin coater, controlling the rotating speed to be 2000r/min, controlling the spin coating time to be 30s, heating the conductive glass substrate to 60 ℃, and spin-coating CH on the substrate by utilizing hot air assistance3NH3PbI3-xClxPrecursor solution, the amount of the spin-coating precursor solution is 30 mu l/cm2Then transferring the mixture into a vacuum drying oven to heat the mixture to 130 ℃, and carrying out annealing treatment for 8 min. And (2) dropwise coating deionized water with the volume of 1.5% of that of the precursor solution on the surface of the annealed film by using a liquid transfer device, wherein the substrate is still in an annealing atmosphere at 130 ℃ in the dropwise coating process, before the deionized water is not completely evaporated, a layer of precursor solution is further spin-coated, the amount of the spin-coated solution is the same as that of the first spin-coating, the annealing time is 60min, after the precursor solution is completely crystallized, the substrate is cooled to room temperature, and the substrate is transferred into a culture dish to be stored in a sealed manner so as to be prevented from being oxidized and decomposed in the air, so that the conductive substrate with the surface covered.
Comparative example 1:
the difference between the comparative example 1 and the example 2 is that deionized water is not dripped on the surface of the perovskite thin film after the first spin-coating annealing in the step (3), and the rest steps are the same as those in the example 2.
Comparative example 2:
comparative example 2 differs from example 2 in three points: firstly, preheating a substrate when spin-coating a precursor solution, and spin-coating the substrate at normal temperature; secondly, only one layer of precursor solution is coated in a spinning mode to carry out annealing treatment to obtain a perovskite film; thirdly, after the precursor solution is spin-coated, deionized water is not added for treatment; the rest of the procedure was the same as in example 2.
The concrete experiment demonstrates that:
SEM images of the perovskite thin films prepared in examples 1 to 3 of the present application were compared with those of the perovskite thin films prepared in comparative examples 1 and 2. As shown in figures 1-5. As shown in fig. 1 to 5, compared with the perovskite thin film prepared by adding deionized water in the step-improved process in comparative example 1 and the perovskite thin film prepared by using the common process in comparative example 2, the perovskite thin film prepared by adding deionized water in examples 1 to 3 has better crystallization effect, the micro-crystallization state is a one-dimensional hollow microtube array structure, the microtube array has more complete morphology and better uniformity, so that the contact area between the microtube array structure and the electron transport layer and the hole transport layer is increased, and the rapid separation and transmission of electrons and holes are facilitated. And in examples 1 to 3, the microstructure morphology of the finished perovskite thin film is best when the volume fraction of the drop-coated deionized water is 1% in example 2.
The XRD patterns of the perovskite thin films prepared in comparative example 1, comparative example 2 and example 2 (as shown in fig. 6) were compared, wherein fig. 6(a) is comparative example 2, i.e.: fig. 6(b) shows a perovskite thin film prepared by a conventional process as comparative example 1, i.e.: a perovskite thin film prepared by a modified process without adding deionized water, fig. 6(c) is example 2, i.e.: an improved process for dispensing deionized water with a volume fraction of 1%. As can be seen in fig. 6: prepared perovskite film generates CH3NH3PbI3And CH3NH3PbCl3Two phases. Example 2 the perovskite thin film with 1% deionized water drop-coated has stronger diffraction peak intensity, and the oriented growth of crystal grains perpendicular to the substrate direction can be obviously seen. From the scherrer equation: calculated as D0.89 lambda/beta cos theta, the crystal grain size increases and then decreases with the increase of the volume fraction of the deionized water, and when the dropping coating amount is 1%, the crystal grain size is the largest, and the crystallinity of the grown micron tube is higher.
PL plots (shown in fig. 7) of the perovskite thin films prepared in comparative examples 1, 2 and 2 were compared, wherein fig. 7(a) is comparative example 2, namely: fig. 7(b) shows a perovskite thin film prepared by a conventional process as comparative example 1, i.e.: a perovskite thin film prepared by a modified process without adding deionized water, fig. 7(c) is example 2, i.e.: an improved process for dispensing deionized water with a volume fraction of 1%. As can be seen in fig. 7: example 2, i.e. (volume fraction of deionized water dropped is 1%), the fluorescence intensity was weaker than that of comparative example 1 in which deionized water was not dropped in the improved process and comparative example 2 in which deionized water was not added in the conventional process. That is to say: deionized water is dripped on the surface of the perovskite film to passivate the surface and the internal defects of the film, and the nonradiative transition process of a current carrier is inhibited, so that the fluorescence intensity is weakened, and the separation and the transmission of the current carrier are facilitated.
The UV-vis patterns (as shown in fig. 8) of the perovskite thin films prepared in comparative example 1, comparative example 2 and example 2 were compared. Wherein, fig. 8(a) is comparative example 2, namely: fig. 8(b) shows a perovskite thin film prepared by a conventional process as comparative example 1, i.e.: a perovskite thin film prepared by a modified process without adding deionized water, fig. 8(c) is example 2, i.e.: an improved process for dispensing deionized water with a volume fraction of 1%. As can be seen in fig. 8: in example 2, compared with comparative examples 1 and 2, the light absorption capacity of the thin film is obviously enhanced, the absorption wavelength of light gradually shifts to the infrared direction, and the band gap of the perovskite thin film is gradually reduced as shown by calculation from the band gap Eg of 1240/lambda. The light absorption cut-off wavelength of the perovskite thin film in the embodiment 2 is 800nm, the corresponding optical band gap is 1.5eV, and the optimal absorption band gap of the light absorption layer of the solar cell is close to 1.4eV, so that the perovskite thin film with the micron tube structure is more beneficial to the absorption of light.
The perovskite thin film with the micron tube array structure prepared by the invention is applied to a plane heterojunction perovskite solar cell for testing, and the performance parameters are shown in the following table 1.
TABLE 1 Performance parameters based on different perovskite light absorbing layer films
(test illumination conditions: AM1.5G, 100 mW/cm)2)
From the above table data, it can be seen that: the open-circuit voltage, the short-circuit current density, the filling factor and the conversion efficiency of the battery are all obviously improved. Example 2 improved Process addition H2Conversion efficiency of O cell with no H addition to the conventional Process of comparative example 2 and the improved Process of comparative example 12The O ratio is obviously improved. The test data result shows that the perovskite light absorption layer film with the microtube array structure is more beneficial to improving the overall performance of the cell.
Claims (8)
1. A preparation method of a perovskite thin film with a microtube array structure is characterized by comprising the following steps:
taking a hard conductive glass substrate, carrying out ultrasonic cleaning on the surface of the hard conductive glass substrate by using acetone, alcohol and deionized water in sequence, then blowing the surface of the hard conductive glass substrate by using a nitrogen gun, and then putting the hard conductive glass substrate into an ozone machine for carrying out ozone treatment for 10-15 min to prepare a conductive glass substrate for later use;
step two, respectively taking CH according to the molar ratio of 1: 1-3: 13NH3I and PbCl2Mixing to prepare a mixed solute, adding an N, N-dimethylformamide solvent into the mixed solute according to the proportion of 0.1-0.3 mol/l between the mixed solute and the solvent, fully stirring and dissolving, placing the obtained mixed solution into an ultrasonic cleaner, and carrying out ultrasonic oscillation treatment for 8-14 h at the temperature of 40-60 ℃ to prepare CH3NH3PbI3-xClxPrecursor solution for later use;
step three, placing the conductive glass substrate prepared in the step one in a spin coater, controlling the temperature of the conductive glass substrate to be 60-70 ℃, controlling the rotating speed of the spin coater to be 2000-3000 r/min, and under the assistance of hot air, according to CH3NH3PbI3-xClxThe area of the precursor solution and the conductive glass substrate to be spin-coated is 30-50 mul/cm2Measuring the CH prepared in the step two3NH3PbI3-xClxSpin-coating the precursor solution on the surface of a conductive glass substrate in a spin coater, then placing the conductive glass substrate in a vacuum drying oven, and annealing for 8-15 min at the temperature of 70-130 ℃ to prepare a primary spin-coated substrate for later use;
step four, adopting a pipettor to measure CH obtained in step three3NH3PbI3-xClxDeionized water with the volume of 0.5-1.5% of the precursor solution is dripped to the surface of the one-time spin-coating substrate in the annealing atmosphere of 70-130 ℃ prepared in the third step, and before the dripped deionized water is not completely evaporated, the deionized water is dripped according to CH3NH3PbI3-xClxThe area of the precursor solution and the substrate to be spin-coated is 30-50 mul/cm2Taking CH prepared in the second step3NH3PbI3-xClxSpin coating the precursor solution on the surface of the primary spin-coated substrate to obtain a secondary spin-coated substrate, and then,and (3) annealing the obtained secondary spin-coating substrate at the temperature of 70-130 ℃ for 30-60 min until the liquid on the surface of the secondary spin-coating substrate is completely crystallized, cooling to room temperature to obtain the conductive substrate with the surface covered with the perovskite thin film with the micron tube array structure, and placing the conductive substrate in a culture dish for sealed storage.
2. The method for preparing a perovskite thin film with a microtube array structure as claimed in claim 1, wherein: in the first step, the conductive glass substrate is FTO transparent conductive glass.
3. The method for preparing a perovskite thin film with a microtube array structure as claimed in claim 1, wherein: in the first step, the time of ultrasonic cleaning is 10-15 min each time.
4. The method for preparing a perovskite thin film with a microtube array structure as claimed in claim 1, wherein: in step three, CH is spin-coated3NH3PbI3-xClxThe operation of the precursor solution needs to be completed within 20-30 s.
5. The method for preparing a perovskite thin film with a microtube array structure as claimed in claim 1, wherein: in the third step, the temperature of the hot air assisted by the hot air is 60-70 ℃.
6. The method for preparing a perovskite thin film with a microtube array structure as claimed in claim 1, wherein: in step four, another CH is selected3NH3PbI3-xClxThe amount of precursor solution and CH spin-coated in step three3NH3PbI3- xClxThe amount of precursor solution was the same.
7. The method according to claim 1, wherein the perovskite thin film has a microtube array structureCharacterized in that: in the fourth step, the amount of deionized water dripped is CH taken in the third step3NH3PbI3-xClx1% of the volume of the precursor solution.
8. The method for preparing a perovskite thin film with a microtube array structure as claimed in claim 1, wherein: in step four, another CH is selected3NH3PbI3-xClxWhen the precursor solution is used for spin coating on the surface of a primary spin coating substrate, the temperature of the primary spin coating substrate needs to be controlled to be 60-70 ℃, the rotating speed of a spin coater needs to be 2000-3000 r/min, and meanwhile, hot air assistance needs to be carried out, and the temperature of the hot air assistance is 60-70 ℃.
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Application publication date: 20180914 Assignee: Shanghai Huanming Information Technology Co.,Ltd. Assignor: HENAN University OF SCIENCE AND TECHNOLOGY Contract record no.: X2024980001050 Denomination of invention: A Preparation Method for Perovskite Thin Films with Microtube Array Structure Granted publication date: 20210625 License type: Common License Record date: 20240123 |