CN110352507A - Preparation method and application of perovskite thin film - Google Patents
Preparation method and application of perovskite thin film Download PDFInfo
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
A preparation method of a perovskite thin film at least comprises the following steps: s01, preheating a substrate and a perovskite precursor solution under an air condition; s02, under the conditions of air and heat radiation, dripping the preheated perovskite precursor solution on the surface of the substrate, and then performing coating treatment on coating equipment; and S03, annealing the substrate obtained by the coating treatment in the step S02 to obtain the perovskite thin film. The method adopts a heat radiation mode, realizes the preparation of the perovskite thin film under the air condition, and the photoelectric conversion efficiency of the obtained perovskite thin film reaches 16.44 percent, and can achieve the technical effect consistent with the photoelectric efficiency of the perovskite thin film prepared in a glove box and in a nitrogen atmosphere.
Description
The invention belongs to the technical field of perovskite thin films, and particularly relates to a preparation method and application of a perovskite thin film.
Since the solar cell using the perovskite material as the light absorption layer, in which the photoelectric conversion efficiency reaches 3.8%, was first prepared by Akihiro Kojima in 2009, research on using the perovskite material as the light absorption layer of the solar cell has been continuously developed. In 2013, on the basis of improving the original process method, the Gratzel research group synthesizes the organic metal halide perovskite-based solar cell with a planar heterojunction structure by using a meteorological deposition method, the efficiency reaches 15 percent, and the efficiency of the organic metal halide perovskite-based solar cell makes a historical breakthrough which is judged as one of ten scientific breakthroughs by the Science journal in the same year. As of 12 months in 2017, research results of photoelectric conversion efficiency reaching 22.7% have been obtained for the research of perovskite solar cells in a glove box under the protection of inert gas. Although the development history is less than 10 years, the photoelectric conversion efficiency of the perovskite solar cell is close to that of monocrystalline silicon, and the perovskite solar cell has a very wide market prospect because the perovskite solar cell is simple in preparation process and low in cost and can be made into a flexible cell.
At present, the film forming technology of the perovskite solar cell mainly comprises methods such as spin coating, blade coating, ink-jet printing, vapor phase assisted deposition and the like. Among the above methods, the perovskite thin film prepared by the spin coating method has uniform compactness and fewer defects, so that the obtained battery has high efficiency, and the spin coating method is a method commonly used by researchers in laboratories.
Since the perovskite substance is decomposed as soon as water and oxygen are encountered, perovskite solar cells are currently manufactured in a nitrogen atmosphere and in a glove box. The glove box preparation process mainly comprises two modes of normal-temperature spin coating (substrate normal temperature and spin coating process normal temperature) and substrate preheating spin coating (the substrate is preheated before spin coating, but is not heated in the spin coating process), although the efficiency of the perovskite solar cell prepared by the glove box spin coating process under the nitrogen atmosphere reaches 22.7% to the maximum, the perovskite solar cell prepared in the glove box under the nitrogen atmosphere has great limitation, and industrialization cannot be realized. In addition, when the spin coating process of the glove box is directly carried to the air for preparing the perovskite solar cell, the efficiency of the obtained cell device is very low. If a normal-temperature spin coating process is adopted in air for spin coating, the surface of the obtained perovskite thin film is shown in fig. 1, and the perovskite thin film obtained from fig. 1 has more holes, which can seriously limit the photoelectric conversion efficiency of the perovskite solar cell. As another example, a substrate is preheated and spin-coated in air, and the surface of the obtained perovskite thin film is as shown in fig. 2, it can be seen from fig. 2 that although the obtained perovskite thin film has fewer holes compared with the normal-temperature spin-coating, the perovskite thin film still has a plurality of holes, which also limits the photoelectric conversion efficiency of the perovskite solar cell.
The technical problem to be solved by the invention is as follows: the preparation method of the perovskite thin film is provided to solve the problems that the existing perovskite thin film cannot be prepared in air, and the perovskite thin film prepared by spin coating in air has many holes, low photoelectric conversion efficiency and the like.
Further, the invention also provides application of the perovskite thin film.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a perovskite thin film at least comprises the following steps:
s01, preheating a substrate and a perovskite precursor solution under an air condition;
s02, under the conditions of air and heat radiation, dripping the preheated perovskite precursor solution on the surface of the preheated substrate, and then performing coating treatment on coating equipment;
and S03, annealing the substrate obtained by the coating treatment in the step S02 to obtain the perovskite thin film.
Correspondingly, the photoelectric device comprises the perovskite thin film, and the perovskite thin film is prepared by the preparation method of the perovskite thin film.
Further, the perovskite solar cell comprises a light absorbing layer, and the light absorbing layer is provided by the preparation method of the perovskite thin film.
Compared with the prior art, the perovskite film is prepared by coating in the air through preheating and heat radiation, the obtained perovskite film has few holes or even no holes, the compactness is good, the photoelectric efficiency reaches 16.44%, and the perovskite film can achieve the effect of being consistent with the photoelectric efficiency of the perovskite film prepared in a glove box in a nitrogen atmosphere under the same structure. In addition, the preparation method is convenient and simple, is suitable for large-scale production, and has practical application significance.
The photoelectric device provided by the invention has the characteristics of few holes or even no holes and good compactness as the device structure comprises the perovskite film prepared by the perovskite film preparation method, so that the photoelectric efficiency of the photoelectric device reaches 16.44%.
According to the perovskite solar cell provided by the invention, as the light absorption layer is prepared by the perovskite thin film preparation method, the light absorption layer has the effect of few holes or even no holes, the good compactness is shown, and the efficiency of the obtained solar cell is up to 16.44%.
FIG. 1 is an SEM image of a perovskite thin film obtained by spin coating in air at a normal temperature through a spin coating process;
FIG. 2 is an SEM image of a perovskite thin film obtained by spin coating of a substrate preheating spin coating process in air;
FIG. 3 is a schematic view of a process flow for preparing a perovskite thin film provided by the present invention;
FIG. 4 is an SEM image of a perovskite thin film prepared in example 1 of the present invention;
FIG. 5 is a comparison of perovskite thin films prepared in comparative example 1, comparative example 2 and inventive example 1;
FIG. 6 is an XRD pattern of perovskite thin films prepared in comparative example 1, comparative example 2 and example 1 of the present invention;
FIG. 7 is a UV-via curve for perovskite solar cells made from perovskite thin films prepared in comparative example 1, comparative example 2 and inventive example 1;
FIG. 8 is a J-V curve of perovskite solar cells fabricated from perovskite thin films prepared in comparative example 1, comparative example 2 and examples 1 to 4 of the present invention;
FIG. 9 is a distribution diagram of photoelectric conversion efficiency of perovskite solar cells made of perovskite thin films prepared in comparative example 1, comparative example 2 and examples 1 to 4 of the present invention;
FIG. 10 is a schematic structural diagram of a perovskite solar cell made of a perovskite thin film prepared in example 1 of the present invention;
wherein, 1-a substrate; 2-a hole transport layer; 3-a light absorbing layer; 4-an electron transport layer; 5-a buffer layer; 6-metal conductive electrode.
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The present invention relates to the noun explanation:
substrate: the material is used for bearing a perovskite precursor, the perovskite precursor forms a perovskite film on the surface of the substrate, and after the perovskite film is formed, the substrate can be removed or retained; in some cases, the substrate and the base are the same meaning, for example, when the perovskite thin film is made into a light absorption layer of a solar cell, the substrate is the base, and in this case, the substrate may be ITO, FTO, PEN, PET, or the like, and may also be ITO, FTO, PEN, PET, or the like that includes a carrier transport layer (which may be a hole transport layer or an electron transport layer).
Referring to fig. 3, the present invention provides a method for preparing a perovskite thin film.
Specifically, the preparation method of the perovskite thin film at least comprises the following steps:
s01, preheating a substrate and a perovskite precursor solution under an air condition;
s02, under the conditions of air and heat radiation, dripping the preheated perovskite precursor solution on the surface of the preheated substrate, and then performing coating treatment on coating equipment;
and S03, annealing the substrate obtained by the coating treatment in the step S02 to obtain the perovskite thin film.
The following explains the preparation method of the perovskite thin film in detail:
the coating equipment can be glue homogenizing equipment and blade coating equipment. In particular, it may be a spin coater or a blade coater. If the spin coater is the spin coater, preheating a suction disc of the spin coater; in the case of a blade coater, the blade and the blade platform need to be preheated simultaneously.
Preferably, the coating equipment can also be subjected to preheating treatment, the temperature of the coating equipment is 70-85 ℃, moisture is remained at too low temperature, the coating of a perovskite precursor is not facilitated, the temperature is too high, and the heat radiation is generated to ensure that the temperature of a strong perovskite precursor is too high to generate non-perovskite minerals.
In the preheating process of the coating equipment, the coating equipment and the substrate can be respectively preheated; the coating device and the substrate can also be placed together and then preheated; the coating apparatus, substrate and perovskite precursor solution may also be preheated together. When the three are placed in the same environment for preheating, the preheating of the three is only needed to be carried out to 70-85 ℃. And if the substrate is preheated separately, the substrate needs to be preheated to 90-110 ℃, the preheating time is at least 10min, and the situation that the preheated substrate is transferred to coating equipment and temperature reduction is caused to be unfavorable for crystallization of a perovskite precursor solution to generate perovskite is avoided.
Preferably, the concentration of the perovskite precursor solution is 0.8-1.5 mmol/mL. The perovskite thin film obtained in the concentration range has good surface compactness and no foam holes, and when the perovskite precursor solution in the concentration range is prepared into the perovskite thin film for the perovskite solar cell, the efficiency can reach 13.48-16.44%.
In the perovskite precursor solution, the perovskite precursor is of a structural formula conforming to ABX3A, B, wherein A is any one of methylamine, methyl diamine, cesium and indium, B is any one of lead and tin, and X is any one of chlorine, bromine and iodine. The solvent of the perovskite precursor solution is Dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). Preferably, the perovskite precursor solution is preheated to 70-85 ℃. The temperature of the solution is consistent with that of the thermal radiation heating, so that the solution and the substrate have small temperature difference or even no temperature difference, and the phenomenon that the film cracks due to stress generated in the crystallization process is avoided.
Further preferably, the perovskite precursor is CH3NH 3PbI 3. The perovskite precursor takes lead acetate as a lead source and methyl amine iodide as a raw material, so that the methyl amine iodide and the lead acetate react to generate CH3NH 3PbI 3. With coproduction of monomethylamine (CH)3NH 2) And acetic acid (CH)3COOH), monomethylamine and acetic acid can be thoroughly volatilized when the coating is carried out in a spin coating mode under the thermal radiation condition, and bubble-shaped holes on the surface of the perovskite film caused by volatilization in the annealing process are avoided.
The heat radiation condition in step S02 of the present invention refers to that the perovskite strong body solution is dropped on the surface of the substrate until the coating process is completed, and the whole process is irradiated by a heat radiation light source. The temperature stability of the whole spin coating process is ensured through the irradiation of a thermal radiation light source, so that the perovskite is directly crystallized in the perovskite precursor solution, other substances generated in the reaction process can be volatilized quickly, the phenomenon that the residual components volatilize in the subsequent annealing process to cause bubble-shaped holes is avoided, and the compactness of the obtained perovskite film is ensured. The purpose of heat radiation is to accelerate solvent volatilization and crystallization, and on the other hand, the volatilized solvent can inhibit water and oxygen from dissolving into the perovskite precursor solution or attaching to the surface of the generated perovskite film to a certain extent so as to resist the damage of water and oxygen to the formed perovskite film; and when the temperature is too high, non-perovskite minerals can be generated.
Preferably, the heat radiation light source may be an incandescent lamp, a halogen tungsten lamp, or the like. In the process of step S02, it is also necessary to sense and monitor the temperature of the substrate surface by using a temperature detector (thermocouple), and when the temperature of the substrate surface changes, the radiation conditions such as the power of the thermal radiation light source, the distance between the thermal radiation light source and the substrate, and the like are adjusted in time, so that the temperature of the substrate surface is equalized. If the coating equipment is spin coating equipment, the thermocouple senses the surface temperature of the substrate and the surface temperature of the sucker of the spin coating equipment, and adjusts the radiation condition of the heat radiation light source to ensure that the temperature is constant or not greatly changed in the spin coating process of the whole spin coating machine.
Preferably, the spin coating speed is 4000 to 8000 r/min. The spin coating speed is too high to control the thickness of the formed film. And under the spin coating speed, the thickness of the obtained perovskite crystal layer is 300-500 nm.
Preferably, the relative humidity of the air of step S02 is less than or equal to 50%. The relative humidity is too high, which is not beneficial to film formation, and the perovskite is easy to be oxidized, thus the performance of the device is reduced.
In step S03, the annealing temperature of the annealing treatment is 90-100 ℃, and the annealing time is 5-10 min. Because the volatile components generated in the spin coating process of the perovskite precursor solution are volatilized under the thermal radiation condition, only a further crystallization process is carried out in the annealing crystallization process without volatilization of the volatile components, bubble-like holes on the surface of the perovskite film due to the fact that the volatilization speed of the volatile components is smaller than the crystallization speed are avoided, and the compact perovskite film finished product obtained after annealing is guaranteed.
According to the preparation method of the perovskite thin film, the perovskite thin film is prepared by coating in the air through preheating and heat radiation, the obtained perovskite thin film has few holes or even no holes, the compactness is good, the photoelectric efficiency reaches 16.44%, and the technical effect that the photoelectric efficiency is consistent with that of the perovskite thin film prepared in a glove box combined nitrogen atmosphere can be achieved. In addition, the preparation method is convenient and simple, is suitable for large-scale production, and has practical application significance.
The invention further provides a photoelectric device on the basis of the preparation method of the perovskite thin film, the photoelectric device at least comprises the perovskite thin film, and the perovskite thin film of the photoelectric device is obtained by adopting the preparation method of the perovskite thin film.
Further, the photoelectric device of the present invention is a perovskite solar cell, and the structure of the perovskite solar cell may be a forward structure or a reverse structure. Wherein, the perovskite solar cell structure of forward structure does: a metal oxide conductive substrate/an electron transport layer/a perovskite thin film layer/a hole transport layer/a metal conductive silver layer; the perovskite solar cell structure of reverse structure does: metal oxide conductive substrate/hole transport layer/perovskite thin film layer/electron transport layer/metal conductive aluminum layer.
In one embodiment, one structure of the perovskite solar cell is shown in fig. 10, and specifically includes a substrate 1, and a hole transport layer 2, a perovskite thin film layer (light absorption layer) 3, an electron transport layer 4, a buffer layer 5, and a metal conductive electrode 6, which are stacked in this order from one surface of the substrate 1 to the outside.
Wherein, the material of the substrate 1 is any one of ITO, FTO, PEN and PET.
The hole transport layer 2 is made of PEDOT, PSS, PEDOT, NiO and PTAA.
The material of the electron transport layer 4 is C60PCBM, etc.
The material of the buffer layer 5 is BCP.
The material of the metal conductive electrode 6 is silver or aluminum.
In one embodiment, the perovskite solar cell is prepared as follows:
(a) ultrasonically cleaning the substrate by using a cleaning solution to obtain a clean substrate;
(b) UV irradiation treatment for 20-30 min;
(c) placing the substrate obtained in the step (b) on a spin coater, and spin-coating a hole transport layer;
(d) placing the substrate containing the hole transport layer obtained in the step (c) on a heating platform, and preheating at 90-110 ℃ for at least 10 min;
(e) preheating the perovskite precursor solution in an environment of 70-85 ℃ for at least 5 min;
(f) placing a thermal radiation light source (such as an incandescent lamp) above the spin coater, adjusting the temperature of the surface of a sucker of the spin coater by controlling the magnitude of current, and monitoring the temperature in real time by using a thermocouple to ensure that the temperature of the surface of the sucker is 70-85 ℃;
(g) continuously radiating heat, controlling the relative humidity of air around the spin coater to be less than or equal to 50%, quickly transferring the preheated substrate in the step (d) onto a sucker of the spin coater, dripping the preheated perovskite precursor solution onto the surface of a cavity transport layer, ensuring the temperature of the substrate to be 70-85 ℃, and immediately performing spin coating treatment at the speed of 4000-8000 r/min to obtain a perovskite layer with the thickness of 300-500 nm;
(h) placing the substrate containing the perovskite layer obtained in the step (g) on a heating platform, annealing at 90-100 ℃, wherein the annealing time is 5-10 min, and then naturally cooling to room temperature;
(i) transferring the substrate containing the perovskite thin film obtained in the step (h) to a thermal evaporation system, and performing evaporation on an electron transmission layer, a buffer layer and a metal conductive electrode on the surface of the perovskite thin film outwards in sequence, wherein the thickness of the evaporated electron transmission layer is 20-40 nm, the thickness of the evaporated buffer layer is 4-10 nm, and the thickness of the metal conductive electrode is 100-200 nm.
To better illustrate the method of fabricating a perovskite thin film provided by embodiments of the present invention, the following is further illustrated by a plurality of examples of fabricating perovskite solar cells.
Example 1
A preparation method of a perovskite solar cell comprises the following steps:
(1) and sequentially adopting a detergent, deionized water, acetone and isopropanol to clean the ITO substrate.
(2) Blowing the ITO substrate cleaned in the step (1) by using nitrogen, and irradiating for 30min by using a UV machine.
(3) And (3) placing the ITO substrate obtained in the step (2) in a spin coater, and spin-coating PEDOT at the speed of 4000 r/min to obtain a hole transport layer with the thickness of 30 nm.
(4) Dissolving methyl amine iodide and lead acetate in DMF at a molar ratio of 3:1 to obtain 1 mmol/mL perovskite precursor solution, placing the perovskite precursor solution on a heating platform, preheating at 80 ℃ for 5min, and filtering with a 0.45 mu m filter head for later use.
(5) Placing the ITO substrate with the hole transport layer obtained in the step (3) on a heating platform, and preheating for 10min at the temperature of 80 ℃.
(6) And an incandescent lamp is added above the commercial spin coater to serve as a heat radiation light source, and a thermocouple is adopted to detect the surface temperature of the sucking disc of the commercial spin coater, so that the surface temperature of the sucking disc is stably maintained at 80 ℃ or above.
(7) Transferring the ITO substrate with the hole transport layer onto the spin coater sucker in the step (6), dropwise adding 50 mu L of the perovskite precursor solution in the step (4) onto the surface of the hole transport layer, carrying out spin coating at the spin coating speed of 4000 r/min for 30 s, and continuously radiating heat by an incandescent lamp in the spin coating process to obtain the perovskite layer coated on the surface of the hole transport layer.
(8) And (5) placing the device obtained in the step (7) on a heating table, annealing at 95 ℃ for 5min, and naturally cooling to room temperature.
(9) Transferring the device obtained in the step (8) to an evaporation chamber, and sequentially evaporating 30 nm of C on the surface of the perovskite layer outwards60(electron transport layer), 8 nm buffer layer (BCP), 100 nm Ag (metal conductive electrode), to this end, the perovskite solar cell of example 1 was obtained.
Example 2
A preparation method of a perovskite solar cell comprises the following steps:
(1) and sequentially adopting a detergent, deionized water, acetone and isopropanol to clean the ITO substrate.
(2) Blowing the ITO substrate cleaned in the step (1) by using nitrogen, and irradiating for 30min by using a UV machine.
(3) And (3) placing the ITO substrate obtained in the step (2) in a spin coater, and spin-coating PEDOT at the speed of 4000 r/min to obtain a hole transport layer with the thickness of 30 nm.
(4) Dissolving methyl amine iodide and lead acetate in DMF at a molar ratio of 3:1 to obtain 0.8 mmol/mL perovskite precursor solution respectively, placing the obtained perovskite precursor solution on a heating platform, preheating at 80 ℃ for 5min, and filtering with a 0.45-micron filter head for later use.
(5) Placing the ITO substrate with the hole transport layer obtained in the step (3) on a heating platform, and preheating for 10min at the temperature of 80 ℃.
(6) And an incandescent lamp is added above the commercial spin coater to serve as a heat radiation light source, and a thermocouple is adopted to detect the surface temperature of the sucking disc of the commercial spin coater, so that the surface temperature of the sucking disc is stably maintained at 80 ℃ or above.
(7) Transferring the ITO substrate with the hole transport layer onto the spin coater sucker in the step (6), dropwise adding 50 mu L of the perovskite precursor solution in the step (4) onto the surface of the hole transport layer, carrying out spin coating at the spin coating speed of 4000 r/min for 30 s, and continuously radiating heat by an incandescent lamp in the spin coating process to obtain the perovskite layer coated on the surface of the hole transport layer.
(8) And (5) placing the device obtained in the step (7) on a heating table, annealing at 95 ℃ for 5min, and naturally cooling to room temperature.
(9) Transferring the device obtained in the step (8) to an evaporation chamber, and sequentially evaporating 30 nm of C on the surface of the perovskite layer outwards60(electron transport layer), 8 nm buffer layer (BCP), 100 nm Ag (metal conductive electrode), to this end, the perovskite solar cell of example 3 was obtained.
Example 3
A preparation method of a perovskite solar cell comprises the following steps:
(1) and sequentially adopting a detergent, deionized water, acetone and isopropanol to clean the ITO substrate.
(2) Blowing the ITO substrate cleaned in the step (1) by using nitrogen, and irradiating for 30min by using a UV machine.
(3) And (3) placing the ITO substrate obtained in the step (2) in a spin coater, and spin-coating PEDOT at the speed of 4000 r/min to obtain a hole transport layer with the thickness of 30 nm.
(4) Dissolving methyl amine iodide and lead acetate in DMF at a molar ratio of 3:1 to obtain 1.2 mmol/mL perovskite precursor solutions respectively, placing the perovskite precursor solutions on a heating platform, preheating at 80 ℃ for 5min, and filtering with a 0.45-micrometer filter head for later use.
(5) Placing the ITO substrate with the hole transport layer obtained in the step (3) on a heating platform, and preheating for 10min at the temperature of 80 ℃.
(6) And an incandescent lamp is added above the commercial spin coater to serve as a heat radiation light source, and a thermocouple is adopted to detect the surface temperature of the sucking disc of the commercial spin coater, so that the surface temperature of the sucking disc is stably maintained at 80 ℃ or above.
(7) Transferring the ITO substrate with the hole transport layer onto the spin coater sucker in the step (6), dropwise adding 50 mu L of the perovskite precursor solution in the step (4) onto the surface of the hole transport layer, carrying out spin coating at the spin coating speed of 4000 r/min for 30 s, and continuously radiating heat by an incandescent lamp in the spin coating process to obtain the perovskite layer coated on the surface of the hole transport layer.
(8) And (5) placing the device obtained in the step (7) on a heating table, annealing at 95 ℃ for 5min, and naturally cooling to room temperature.
(9) Transferring the device obtained in the step (8) to an evaporation chamber, and sequentially evaporating 30 nm of C on the surface of the perovskite layer outwards60(electron transport layer), 8 nm buffer layer (BCP), 100 nm Ag (metal conductive electrode), to this end, the perovskite solar cell of example 3 was obtained.
Example 4
A preparation method of a perovskite solar cell comprises the following steps:
(1) and sequentially adopting a detergent, deionized water, acetone and isopropanol to clean the ITO substrate.
(2) Blowing the ITO substrate cleaned in the step (1) by using nitrogen, and irradiating for 30min by using a UV machine.
(3) And (3) placing the ITO substrate obtained in the step (2) in a spin coater, and spin-coating PEDOT at the speed of 4000 r/min to obtain a hole transport layer with the thickness of 30 nm.
(4) Dissolving methyl amine iodide and lead acetate in DMF at a molar ratio of 3:1 to obtain 1.5mmol/mL perovskite precursor solutions respectively, placing the perovskite precursor solutions on a heating platform, preheating at 80 ℃ for 5min, and filtering with a 0.45-micron filter head for later use.
(5) Placing the ITO substrate with the hole transport layer obtained in the step (3) on a heating platform, and preheating for 10min at the temperature of 80 ℃.
(6) And an incandescent lamp is added above the commercial spin coater to serve as a heat radiation light source, and a thermocouple is adopted to detect the surface temperature of the sucking disc of the commercial spin coater, so that the surface temperature of the sucking disc is stably maintained at 80 ℃ or above.
(7) Transferring the ITO substrate with the hole transport layer onto the spin coater sucker in the step (6), dropwise adding 50 mu L of the perovskite precursor solution in the step (4) onto the surface of the hole transport layer, carrying out spin coating at the spin coating speed of 4000 r/min for 30 s, and continuously radiating heat by an incandescent lamp in the spin coating process to obtain the perovskite layer coated on the surface of the hole transport layer.
(8) And (5) placing the device obtained in the step (7) on a heating table, annealing at 95 ℃ for 5min, and naturally cooling to room temperature.
(9) Transferring the device obtained in the step (8) to an evaporation chamber, and sequentially evaporating 30 nm of C on the surface of the perovskite layer outwards60(electron transport layer), 8 nm buffer layer (BCP), 100 nm Ag (metal conductive electrode), to this end, the perovskite solar cell of example 4 was obtained.
Comparative example 1
A preparation method of a perovskite solar cell comprises the following steps:
(1) and sequentially adopting a detergent, deionized water, acetone and isopropanol to clean the ITO substrate.
(2) Blowing the ITO substrate cleaned in the step (1) by using nitrogen, and irradiating for 30min by using a UV machine.
(3) And (3) placing the ITO substrate obtained in the step (2) in a spin coater, and spin-coating PEDOT at the speed of 4000 r/min to obtain a hole transport layer with the thickness of 30 nm.
(4) Dissolving methyl amine iodide and lead acetate in DMF at a molar ratio of 3:1 to obtain 1 mmol/mL perovskite precursor solution, placing the perovskite precursor solution on a heating platform, preheating at 80 ℃ for 5min, and filtering with a 0.45 mu m filter head for later use.
(5) And (3) placing the ITO substrate with the hole transport layer obtained in the step (3) on a spin coater, dropwise adding 50 mu L of the perovskite precursor solution obtained in the step (4) to the surface of the hole transport layer, and carrying out spin coating at the spin coating speed of 4000 r/min for 30 s to obtain the perovskite layer coated on the surface of the hole transport layer.
(6) And (3) placing the device obtained in the step (5) on a heating table, annealing at 95 ℃ for 5min, and naturally cooling to room temperature.
(7) Transferring the device obtained in the step (6) to an evaporation chamber, and sequentially evaporating 30 nm of C on the surface of the perovskite layer outwards60(electron transport layer), buffer layer (BCP) of 8 nm, Ag (metal conductive electrode) of 100 nm, thus obtaining the perovskite solar cell of comparative example 1.
Comparative example 2
A preparation method of a perovskite solar cell comprises the following steps:
(1) and sequentially adopting a detergent, deionized water, acetone and isopropanol to clean the ITO substrate.
(2) Blowing the ITO substrate cleaned in the step (1) by using nitrogen, and irradiating for 30min by using a UV machine.
(3) And (3) placing the ITO substrate obtained in the step (2) in a spin coater, and spin-coating PEDOT at the speed of 4000 r/min to obtain a hole transport layer with the thickness of 30 nm.
(4) Dissolving methyl amine iodide and lead acetate in DMF at a molar ratio of 3:1 to obtain 1 mmol/mL perovskite precursor solution, placing the perovskite precursor solution on a heating platform, preheating at 80 ℃ for 5min, and filtering with a 0.45 mu m filter head for later use.
(5) Placing the ITO substrate with the hole transport layer obtained in the step (3) on a heating table, and preheating for 10min at 100 ℃.
(6) And (3) placing the preheated substrate obtained in the step (5) in a spin coater, keeping the temperature of the substrate at 100 ℃, dropwise adding 50 mu L of the perovskite precursor solution obtained in the step (4) to the surface of the hole transport layer, carrying out spin coating at the spin coating speed of 4000 r/min for 30 s, and obtaining the perovskite layer coated on the surface of the hole transport layer.
(7) And (5) placing the device obtained in the step (6) on a heating table, annealing at 95 ℃ for 5min, and naturally cooling to room temperature.
(8) Transferring the device obtained in the step (7) to an evaporation chamber, and sequentially evaporating 30 nm of C on the surface of the perovskite layer outwards60(electron transport layer), buffer layer (BCP) of 8 nm, Ag (metal conductive electrode) of 100 nm, to this end, the perovskite solar cell of comparative example 2 was obtained.
In order to better illustrate the performance of the perovskite thin film prepared by the preparation method of the perovskite thin film, the perovskite thin film and the perovskite solar cell obtained in the examples and the comparative examples are subjected to related performance tests, and the test items comprise micro-morphology, XRD, UV-via curve, J-V curve and photoelectric conversion efficiency.
(1) The micro-morphology: respectively testing the micro-morphology of the perovskite thin films obtained after annealing in the embodiment 1, the comparative example 1 and the comparative example 2 by adopting a scanning electron microscope, and specifically showing in detail in a figure 1, a figure 2 and a figure 4; meanwhile, a general pixel camera is adopted for photographing in the spin coating process, and the detailed description is shown in fig. 5.
As can be seen from the comparison of the SEM images in fig. 1, 2, and 4, the perovskite thin film prepared by the preparation method of the present invention has fewer bubble-shaped holes and smaller hole diameter than those in fig. 1 and 2, and has better micro-morphology integrity; as can be seen from fig. 5, the apparent color of example 1 of the present invention is dark brown, which is darker than the colors of comparative examples 1 and 2, and illustrates that perovskite is crystallized from perovskite precursors during spin coating of example 1 of the present invention, while the perovskite is crystallized during annealing of comparative examples 1 and 2. The perovskite thin film prepared by the method has good microcosmic surface consistency, so that the perovskite thin film obtained in the embodiments 2-4 is not subjected to corresponding SEM scanning test.
(2) XRD phase analysis: the substance corresponding to the 12.8 degree peak is lead iodide, i.e. the decomposition product of perovskite, and it can be seen from the figure that there is almost no lead iodide peak in the perovskite thin film prepared by the heat radiation method, which indicates that the obtained perovskite is not decomposed by the preparation in air, while the other two perovskite thin films have the lead iodide peak, which indicates that the perovskite is partially decomposed. XRD results show that the thermal radiation method can completely convert the precursor into perovskite, and the damage of water and oxygen to the perovskite is avoided to a certain extent.
(3) UV-via curve analysis: the perovskite solar cells obtained in example 1, comparative example 1 and comparative example 2 were subjected to UV-via curve test using an ultraviolet-visible spectrometer, and the test results are shown in fig. 7. As can be seen from fig. 7, the film prepared by the thermal radiation method has better absorption performance for visible light, which is one of the reasons why the device prepared by the thermal radiation method has higher current than the other two methods.
(4) J-V Curve analysis: the perovskite solar cells obtained in examples 1 to 4, comparative example 1 and comparative example 2 were subjected to a J-V curve test using am1.5g solar spectrum, and the test results are shown in fig. 8.
As can be seen from fig. 8, the Open-circuit Voltage (abbreviated as V) of the perovskite solar cell obtained in example 1 of the present inventionOC) 0.958V, Short-circuit Current (Short-circuit Current sensitivity, abbreviated as J)SC) Is 22.26 mA/cm272.51% of Fill Factor (FF for short); cell performance parameters in example 2: voc = 0.93V, Jsc =18.84 mA/cm2FF = 76.88%; cell performance parameters for example 3: voc = 0.92V, Jsc =22.91 mA/cm2FF = 77.99%; cell performance parameters for example 4: voc =0.90V, Jsc =21.70 mA/cm2FF = 79.94%. In comparative example 1, VOC=0.90 V、J SC=2.03 mA/cm 2FF = 75.93%; in comparative example 2, VOC=0.97 V、J SC=15.63 mA/cm 2、FF=70.35%。
As can be seen from the photoelectric conversion efficiency graph of fig. 9, the perovskite solar cell Photoelectric Conversion Efficiencies (PCEs) of embodiments 1 to 4 of the present invention are 15.47%, 13.48%, 16.44%, and 15.69%, respectively; PCE =1.40% for comparative example 1 and 10.68% for comparative example 2. Therefore, the invention can increase the heat radiation under the air condition, and the photoelectric conversion efficiency of the obtained perovskite solar cell is higher than that under the air condition without increasing the heat radiation.
Under conventional conditions, perovskite thin films are prepared in a glove box in combination with a nitrogen atmosphere. The photoelectric efficiency of the perovskite solar cell obtained by combining the preparation of the perovskite thin film in the nitrogen atmosphere in the glove box only reaches 16.2%, while the photoelectric conversion efficiency of the perovskite solar cell obtained by increasing the heat radiation under the air condition reaches 16.44%, which shows that the invention realizes the breakthrough from the preparation of the perovskite thin film in the glove box under the nitrogen condition to the preparation of the perovskite thin film under the air condition, namely the industrialization can be realized.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (13)
- A preparation method of a perovskite thin film is characterized by comprising the following steps: at least comprises the following steps:s01, preheating a substrate and a perovskite precursor solution under an air condition;s02, under the conditions of air and heat radiation, dripping the preheated perovskite precursor solution on the surface of the substrate, and then performing coating treatment on coating equipment;and S03, annealing the substrate obtained by the coating treatment in the step S02 to obtain the perovskite thin film.
- The method for producing a perovskite thin film as claimed in claim 1, wherein: the heat radiation condition is a heat radiation light source.
- The method for producing a perovskite thin film as claimed in any one of claims 1 to 2, wherein: the preheating temperature of the perovskite precursor solution is 70-85 ℃.
- The method for producing a perovskite thin film as claimed in any one of claims 1 to 2, wherein: the concentration of the perovskite precursor solution is 0.8-1.5 mmol/mL.
- The method for producing a perovskite thin film as claimed in claim 1, wherein: the coating mode is spin coating or blade coating.
- The method for producing a perovskite thin film as claimed in any one of claims 1 to 2, wherein: the structural general formula of the perovskite precursor in the perovskite precursor solution is ABX3Wherein A is any one of methylamine, methyl diamine, cesium and indium, B is any one of lead and tin, and X is any one of chlorine, bromine and iodine; the solvent of the perovskite precursor solution is dimethylformamide or dimethyl sulfoxide.
- The method for producing a perovskite thin film as claimed in claim 1, wherein: the relative humidity of the air is less than or equal to 50 percent.
- The method for producing a perovskite thin film as claimed in claim 1, wherein: the preheating temperature of the substrate is 90-110 ℃.
- The method for producing a perovskite thin film as claimed in claim 1, wherein: the temperature of the annealing treatment is 90-100 ℃.
- An optoelectronic device comprising a perovskite thin film, characterized in that: the perovskite thin film is obtained by the method for preparing a perovskite thin film according to any one of claims 1 to 9.
- A perovskite solar cell comprising a light absorbing layer, characterized in that: the light absorbing layer is a perovskite thin film obtained by the method for preparing a perovskite thin film according to any one of claims 1 to 9.
- The perovskite solar cell of claim 11, wherein: the perovskite solar cell has a forward structure or a reverse structure.
- The perovskite solar cell of claim 11 or 12, wherein: the perovskite solar cell is structurally characterized in that the perovskite solar cell is composed of a metal oxide conductive substrate, an electron transmission layer, a perovskite thin film layer, a hole transmission layer and a metal conductive silver layer; or a metal oxide conductive substrate/hole transport layer/perovskite thin film layer/electron transport layer/metal conductive aluminum layer.
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| CN111235635A (en) * | 2020-03-02 | 2020-06-05 | 广西大学 | Growth method of spin-coating single crystal on wide-bandgap semiconductor substrate |
| CN111640868B (en) * | 2020-05-13 | 2022-07-22 | 上海大学 | Preparation method of perovskite thin film photoelectric device based on electronic irradiation modification |
| CN111640868A (en) * | 2020-05-13 | 2020-09-08 | 上海大学 | Preparation method of perovskite thin film photoelectric device based on electronic irradiation modification |
| CN111584717A (en) * | 2020-05-15 | 2020-08-25 | 浙江大学 | Method for improving efficiency of organic-inorganic hybrid perovskite solar cell by aid of photo-thermal combined external field |
| CN111584717B (en) * | 2020-05-15 | 2022-05-10 | 浙江大学 | Method for improving efficiency of hybrid perovskite solar cell by aid of photo-thermal combined external field |
| CN112510157A (en) * | 2020-11-12 | 2021-03-16 | 深圳市惠能材料科技研发中心(有限合伙) | Method for preparing perovskite solar cell in large area through all air |
| CN112748218A (en) * | 2020-12-20 | 2021-05-04 | 浙江大学 | On-line real-time monitoring system for preparing perovskite semiconductor photoelectric device |
| CN112993156A (en) * | 2021-02-04 | 2021-06-18 | 大连理工大学 | Flexible gate with high switching frequency and preparation method thereof |
| CN112993156B (en) * | 2021-02-04 | 2024-03-29 | 大连理工大学 | Flexible gate with high switching times and preparation method thereof |
| CN113193128A (en) * | 2021-05-24 | 2021-07-30 | 电子科技大学 | Perovskite solar cell with interface modification layer and preparation method thereof |
| CN114597314A (en) * | 2022-01-25 | 2022-06-07 | 成都钛钙新能源科技有限公司 | Preparation method of efficient perovskite solar cell with stable full-spectrum light |
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