CN113113541B - Method for passivating perovskite solar cell interface defects by using sodium bistrifluoromethylsulfonylimide - Google Patents
Method for passivating perovskite solar cell interface defects by using sodium bistrifluoromethylsulfonylimide Download PDFInfo
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Abstract
The invention discloses a method for passivating interface defects of a perovskite solar cell by using sodium bistrifluoromethylsulfonyl imide, which belongs to the technical field of perovskite solar cells and comprises the following steps of: s1, cleaning etched FTO conductive glass, S2, and TiO 2 Uniformly spreading the quantum dot solution on the surface of FTO conductive glass to prepare an electron transport layer, transferring the spin-coated film into a muffle furnace, sintering at 450 ℃ for 30min, S3, cooling to room temperature, and preparing the film on the surface of the FTO conductive glass 2 The film was spin coated with a solution of NaTFSI in acetonitrile. In the invention, solution spin coating is adopted to coat TiO on a plane 2 And a layer of NaTFSI is prepared on the film and used for modifying the interface between the electron transport layer and the perovskite and assembling the interface into PSCs, and the NaTFSI modification layer not only can improve the crystallinity of the perovskite film and reduce the non-radiative recombination loss of the perovskite film, but also can optimize the energy level structure of the ETL surface so that the ETL surface is more matched with the energy level of the perovskite, thereby accelerating the extraction and transmission efficiency of electrons between interfaces.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a method for passivating interface defects of a perovskite solar cell by using sodium bistrifluoromethylsulfonylimide.
Background
Organic-inorganic hybrid Perovskite Solar Cells (PSCs) are considered as one of the most promising new types of solar cells, whose Photoelectric Conversion Efficiency (PCE) is rapidly increased from the first reported 3.8% to the present 25.5%. Perovskite type crystal (ABX) 3 ) There are many perovskite crystals as light absorbing active materials in solar cells, the a-site ions of which include the organic cation methylamine (CH 3 NH 3 + ,MA + ) Formamidine (nh=chnh) 3 + ,FA + ) Inorganic cations Cs + Etc.; the divalent metal ion B includes Pb 2+ 、Sn 2+ Etc., and X ions are typically halide ions, e.g. I - 、Br - Cl-, etc. The perovskite material has the advantages of high absorption coefficient, long carrier diffusion length, wide absorption range and the like, so that the perovskite material has wide application in photoelectric devices.
In conventional PSCs device structures, there are conductive glass substrates, electron Transport Layers (ETLs), hole Transport Layers (HTLs), metal electrodes, and the like, in addition to the perovskite photoactive layer. The ETL can promote the extraction of electrons, effectively reduce the energy barrier of electrons from the perovskite light absorption layer to the anode, and play a role in blocking holes, and the quality of the ETL is often one of main factors for determining the performance of PSCs devices. TiO (titanium dioxide) 2 Materials are the most common electron transport materials in PSCs due to their high electron injection rate, stable chemistry, and low cost. However, tiO prepared by solution method 2 The surface of the thin film has a large number of defects, and the defects can cause non-radiative recombination of carriers at the interface of the perovskite layer and the ETL to block charge transmission, so that further improvement of the device PCE is severely restricted, and in addition, attenuation and hysteresis of the device efficiency are induced by the non-radiative recombination.
Disclosure of Invention
The invention aims to provide a method for passivating interface defects of perovskite solar cells by using sodium bistrifluoromethylsulfonyl imide, which adopts a solution spin-coating method to realize TiO (titanium dioxide) on a plane 2 And a layer of NaTFSI is prepared on the film and used for modifying the interface between the electron transport layer and the perovskite and assembling the interface into PSCs, and the NaTFSI modification layer not only can improve the crystallinity of the perovskite film and reduce the non-radiative recombination loss of the perovskite film, but also can optimize the energy level structure of the ETL surface so that the ETL surface is more matched with the energy level of the perovskite, thereby accelerating the extraction and transmission efficiency of electrons between interfaces.
In order to achieve the above effects, the present invention provides the following technical solutions: a method for passivating perovskite solar cell interface defects with sodium bistrifluoromethylsulfonylimide, comprising the steps of:
s1, cleaning the etched FTO conductive glass.
S2, tiO 2 The quantum dot solution is uniformly spread on the surface of the FTO conductive glass to prepare an electron transport layer, and the spin-coated film is transferred into a muffle furnace to be sintered for 30min at 450 ℃.
S3, cooling to room temperature, and adding TiO 2 The film was spin coated with a solution of NaTFSI in acetonitrile.
S4, placing the coated glass in a muffle furnace after spin coating, sintering for 30min at 450 ℃, cooling to room temperature, transferring to a plasma cleaning instrument, and carrying out plasma treatment for 10min.
S5, feeding the treated FTO conductive glass into a glove box, and dripping perovskite precursor liquid on the NaTFSI interface layer to prepare a perovskite layer.
S6, transferring the film to a heating table, and treating for 60min at the temperature of 100 ℃.
S7, cooling to room temperature, spreading the Spiro-OMeTAD solution on a perovskite film for spin coating, and placing the perovskite film in a dampproof cabinet with humidity less than 15% for oxidation for 12 hours after spin coating is finished.
Further, the method further comprises the following steps:
oxidizing in dampproof cabinet for 12 hr, and vacuum coating in a high vacuum coater with vacuum degree less than 6.0X10 -4 Shape of PaAnd evaporating an 80nm gold counter electrode in a state to complete the assembly of the battery.
Further, in the step S1, the etched FTO conductive glass is cleaned, which includes the following steps:
s101, cleaning the etched FTO conductive glass with a cleaning agent, then sequentially placing the conductive glass in absolute ethyl alcohol, acetone and isopropanol for ultrasonic cleaning for 30min each time, taking out, and drying residual solvent on the surface with nitrogen.
S102, placing the dried FTO conductive glass into an ultraviolet ozone cleaner, treating for 20min, placing into a plasma cleaner, cleaning for 5min, and taking out for later use.
Further, in the step S2, spin coating was performed at 700rpm for 5S and at 4000rpm for 20S, respectively.
Further, in the step S5, the preparation method of the perovskite precursor solution includes:
0.5290g of PbI were weighed out in a glove box 2 ，0.0743g PbBr 2 0.0176g CsI,0.1874gFAI and 0.0157g MABr were dissolved in a mixed solution of 0.2mL DMSO and 0.8mL DMF, and stirred until completely dissolved, to prepare a perovskite precursor solution.
Further, in the step S7, the preparation method of the Spiro-ome tad solution comprises the steps of:
72.3mg of Spiro-OMeTAD was weighed in a glove box, dissolved in 1mL of chlorobenzene, stirred until completely dissolved, 17.5. Mu.L of LiTFSI solution and 28.8. Mu.L of 4-tBP were added, and stirred uniformly to prepare a Spiro-OMeTAD solution.
Further, in the step S7, the anti-solvent chlorobenzene was added dropwise at 25S, respectively, at 1000rpm for 10S, at 6500rpm for 20S.
The invention provides a method for passivating perovskite solar cell interface defects by using sodium bistrifluoromethylsulfonyl imide, which has the following beneficial effects:
in the invention, solution spin coating is adopted to coat TiO on a plane 2 A layer of NaTFSI is prepared on the film to modify the interface between the electron transport layer and the perovskite and assemble it into PSCs. N (N)The aTFSI modification layer not only can improve the crystallinity of the perovskite film and reduce the non-radiative recombination loss of the perovskite film, but also can optimize the energy level structure of the ETL surface so that the ETL surface energy level is more matched with the perovskite energy level, thereby accelerating the extraction and transmission efficiency of electrons between interfaces.
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FIG. 1 is a flow chart of a method for passivating perovskite solar cell interface defects with sodium bistrifluoromethylsulfonylimide.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments, and that all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments in the present invention are within the protection scope of the present invention.
The invention provides a technical scheme that: referring to fig. 1, a method for passivating perovskite solar cell interface defects by using sodium bistrifluoromethylsulfonyl imide comprises the following steps:
step one, cleaning the etched FTO conductive glass.
Cleaning the etched FTO conductive glass, which comprises the following steps:
101 Cleaning the etched FTO conductive glass with a cleaning agent, then sequentially placing the conductive glass in absolute ethyl alcohol, acetone and isopropanol for ultrasonic cleaning for 30min each time, taking out, and drying residual solvent on the surface with nitrogen.
102 And (3) placing the dried FTO conductive glass into an ultraviolet ozone cleaning machine, treating for 20min, placing into a plasma cleaning instrument, cleaning for 5min, and taking out for later use.
Step two, tiO is carried out 2 The quantum dot solution is uniformly spread on the surface of the FTO conductive glass to prepare an electron transport layer, and the spin-coated film is transferred into a muffle furnace to be sintered for 30min at 450 ℃.
Wherein, the spin coating is respectively carried out for 5s under the condition of 700rpm and for 20s under the condition of 4000 rpm.
Step three, cooling to room temperature, and finally obtaining the TiO 2 The film was spin coated with a solution of NaTFSI in acetonitrile.
And fourthly, placing the coated glass into a muffle furnace after spin coating, sintering for 30min at 450 ℃, cooling to room temperature, transferring to a plasma cleaning instrument, and carrying out plasma treatment for 10min.
And fifthly, feeding the treated FTO conductive glass into a glove box, and dripping perovskite precursor liquid on the NaTFSI interface layer to prepare a perovskite layer.
The preparation method of the perovskite precursor liquid comprises the following steps:
0.5290g of PbI were weighed out in a glove box 2 ，0.0743g PbBr 2 0.0176g CsI,0.1874gFAI and 0.0157g MABr were dissolved in a mixed solution of 0.2mL DMSO and 0.8mL DMF, and stirred until completely dissolved, to prepare a perovskite precursor solution.
And step six, transferring the film to a heating table, and treating for 60min at the temperature of 100 ℃.
And step seven, cooling to room temperature, spreading the Spiro-OMeTAD solution on a perovskite film for spin coating, and placing the perovskite film in a dampproof cabinet with humidity less than 15% for oxidation for 12 hours after spin coating is finished.
The preparation method of the Spiro-OMeTAD solution comprises the following steps:
72.3mg of Spiro-OMeTAD was weighed in a glove box, dissolved in 1mL of chlorobenzene, stirred until completely dissolved, 17.5. Mu.L of LiTFSI solution and 28.8. Mu.L of 4-tBP were added, and stirred uniformly to prepare a Spiro-OMeTAD solution.
Wherein, the spinning is respectively carried out for 10s under the condition of 1000rpm, for 20s under the condition of 6500rpm, and the anti-solvent chlorobenzene is dripped in the 25 th s.
Step eight, after being oxidized for 12 hours in the dampproof cabinet, the dampproof cabinet is put into a high vacuum coating machine, and the vacuum degree is less than 6.0x10 -4 And evaporating an 80nm gold counter electrode under the Pa state to complete the assembly of the battery.
TiO before and after modification of NaTFSI 2 The properties of the electron transport layers are compared and are shown in Table 1:
table 1: naTFSI modified TiO 2 Energy level of electron transport layerParameters (parameters)
As can be seen from Table 1, naTFSI modified TiO 2 Defect reduction and energy level matching at the interface of the electron transport layer and the perovskite layer.
The perovskite thin film after NaTFSI treatment becomes more uniform, has larger-sized crystal grains and fewer crystal boundaries, and the existence of NaTFSI can have favorable influence on the growth of perovskite crystals, so that the quality of the perovskite thin film is improved, and the cross sections of the device before and after NaTFSI treatment are respectively analyzed.
The size of the perovskite crystal grain of the upper layer can be increased by modifying the titanium dioxide ETL through the NaTFSI interface layer, the crystal boundary is reduced, so that the interface carrier recombination is reduced, the conductivity of the ETL modified by the NaTFSI is enhanced, the work function is reduced, and the device efficiency is obviously improved from 18.62% to 19.83% by optimizing the NaTFSI surface layer.
In the invention, solution spin coating is adopted to coat TiO on a plane 2 A layer of NaTFSI is prepared on the film to modify the interface between the electron transport layer and the perovskite and assemble it into PSCs. The NaTFSI modification layer not only can improve the crystallinity of the perovskite film and reduce the non-radiative recombination loss of the perovskite film, but also can optimize the energy level structure of the ETL surface so that the ETL surface energy level is more matched with the perovskite level, thereby accelerating the extraction and transmission efficiency of electrons between interfaces.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A method for passivating perovskite solar cell interface defects by using sodium bistrifluoromethylsulfonylimide, which is characterized by comprising the following steps:
s1, cleaning etched FTO conductive glass;
s2, tiO 2 Uniformly spreading the quantum dot solution on the surface of the FTO conductive glass to prepare an electron transport layer, transferring the spin-coated film into a muffle furnace, and sintering for 30min at 450 ℃;
s3, cooling to room temperature, and adding TiO 2 Spin coating NaTFSI acetonitrile solution on the film;
s4, placing the coated glass in a muffle furnace after spin coating, sintering for 30min at 450 ℃, cooling to room temperature, transferring to a plasma cleaning instrument, and carrying out plasma treatment for 10min;
s5, feeding the treated FTO conductive glass into a glove box, and dripping perovskite precursor liquid on a NaTFSI interface layer to prepare a perovskite layer;
s6, transferring the film to a heating table, and treating for 60min at the temperature of 100 ℃;
s7, cooling to room temperature, spreading the Spiro-OMeTAD solution on a perovskite film for spin coating, and placing the perovskite film in a dampproof cabinet with humidity less than 15% for oxidation for 12 hours after spin coating is finished.
2. A method of passivating perovskite solar cell interface defects with sodium bistrifluoromethylsulfonylimide as defined in claim 1, further comprising:
oxidizing in dampproof cabinet for 12 hr, and vacuum coating in a high vacuum coater with vacuum degree less than 6.0X10 -4 And evaporating an 80nm gold counter electrode under the Pa state to complete the assembly of the battery.
3. The method for passivating perovskite solar cell interface defects with sodium bistrifluoromethylsulfonylimide according to claim 1, wherein in said step S1, the etched FTO conductive glass is cleaned, comprising the steps of:
s101, cleaning etched FTO conductive glass with a cleaning agent, then sequentially placing the conductive glass in absolute ethyl alcohol, acetone and isopropanol for ultrasonic cleaning for 30min each time, taking out, and drying residual solvent on the surface with nitrogen;
s102, placing the dried FTO conductive glass into an ultraviolet ozone cleaner, treating for 20min, placing into a plasma cleaner, cleaning for 5min, and taking out for later use.
4. A method for passivating perovskite solar cell interface defects as defined in claim 1, wherein in said step S2, the perovskite solar cell interface defects are spin-coated at 700rpm for 5S and at 4000rpm for 20S, respectively.
5. The method for passivating perovskite solar cell interface defects with sodium bistrifluoromethylsulfonylimide according to claim 1, wherein in the step S5, the preparation method of the perovskite precursor solution is as follows:
0.5290gPbI was weighed out in a glove box 2 ，0.0743g PbBr 2 0.0176g CsI,0.1874g FAI and 0.0157g MABr were dissolved in a mixed solution of 0.2ml of LDMSO and 0.8ml of LDMF, and stirred until completely dissolved, to prepare a perovskite precursor solution.
6. The method for passivating perovskite solar cell interface defects with sodium bistrifluoromethylsulfonylimide according to claim 1, wherein in the step S7, the preparation method of the Spiro-ome tad solution is as follows:
72.3mg of Spiro-OMeTAD was weighed in a glove box, dissolved in 1mL of chlorobenzene, stirred until completely dissolved, then 17.5. Mu.L of LLiTFSI solution and 28.8. Mu.L of 4-tBP were added, and stirred uniformly to prepare a Spiro-OMeTAD solution.
7. The method for passivating perovskite solar cell interface defects by using sodium bistrifluoromethylsulfonylimide according to claim 1, wherein in the step S7, the anti-solvent chlorobenzene is added dropwise at the 25 th step after spin-coating under the condition of 1000rpm for 10S, 6500rpm for 20S.
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