CN115843189A - Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains - Google Patents
Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains Download PDFInfo
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- CN115843189A CN115843189A CN202211652239.8A CN202211652239A CN115843189A CN 115843189 A CN115843189 A CN 115843189A CN 202211652239 A CN202211652239 A CN 202211652239A CN 115843189 A CN115843189 A CN 115843189A
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Abstract
The invention discloses a method for improving the performance of a perovskite solar cell through secondary growth of perovskite crystal grains, which comprises the following specific operations: cleaning a transparent conductive substrate, spin-coating a film on the surface of the substrate, continuously spin-coating a perovskite precursor solution on the film, spin-coating a mercaptoethyl acetate/isopropanol solution on the surface of the annealed perovskite film, and obtaining PVK grains with larger grain sizes by a secondary annealing mode, so that the existence of a high defect state density grain boundary is reduced, and the efficient transmission of current carriers is facilitated; meanwhile, due to the existence of sulfydryl and carbonyl functional groups in ET molecules, defect states existing on the surface of PVK are effectively passivated, the performance of the PVK film is further improved, and finally the performance of the perovskite solar cell device processed based on ET/IPA is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a method for improving the performance of a perovskite solar cell through secondary growth of perovskite crystal grains.
Background
Solar energy has been widely used in the field of photovoltaic power generation as a clean energy source. Solar cells have proven to be an effective means of photoelectric conversion as a medium for converting solar energy into electrical energy. Perovskite materials have been successfully applied as novel photoelectric conversion materials in the preparation of solar cells. For perovskite solar cells, the development bottlenecks faced by the perovskite solar cells at present mainly include that the photoelectric conversion efficiency still has a larger promotion space from the theoretical efficiency limit value; meanwhile, due to the ionic characteristics of the perovskite material, a large number of defect points (such as uncoordinated lead ions) exist at the grain boundary of the film-formed surface of the perovskite material, and the defect points can be used as main invasion sites for corroding the perovskite by external factors (water and oxygen), so that the stability of the perovskite film is influenced.
In view of this, the passivation strategy of the surface defects of perovskite is often used by researchers as an effective method for improving the performance of perovskite solar cells. However, the passivation of functional small molecules can only modify defect points existing at the grain boundary of the perovskite thin film, but has the effect of reducing the generation of the grain boundary of the perovskite thin film.
Disclosure of Invention
The technical problems solved by the invention are as follows: the method is limited in that functional small molecules can passivate the surface defects of the perovskite at present, namely, only existing defects at grain boundaries can be passivated, but the existence of the grain boundaries per se cannot be reduced. In view of the above technical problems, the present invention aims to provide a method for improving the performance of a perovskite solar cell through the secondary growth of perovskite crystal grains.
According to the invention, ET molecules are introduced into the surface of the annealed perovskite thin film, and perovskite crystal grains with larger grain sizes are obtained in a secondary annealing mode, so that the existence of grain boundaries is effectively reduced, and the amount of defect points is reduced.
The specific technical scheme is as follows:
a method for improving the performance of a perovskite solar cell through secondary growth of perovskite crystal grains specifically comprises the following operations:
1) Sequentially cleaning a transparent conductive substrate by using deionized water, acetone, ethanol and isopropanol, drying the cleaned substrate, treating by using plasma equipment, and standing at normal temperature for later use;
2) Spin coating a layer of film on the surface of the substrate, wherein the film is PTAA, PEDOT, PSS, niOX and TiO 2 、SnO 2 、ZnO 2 、C 60 、C 70 、PC 61 One or more composite films in the BM;
3) Weighing PbI 2 、PbBr 2 CsI, csBr and FAI, and preparing a perovskite precursor solution, wherein the perovskite precursor solution is FA 0.8 Cs 0.2 PbI 2.85 Br 0.15 Depositing the perovskite precursor solution on the surface of the film in the step 2) in one or more modes of spin coating, blade coating, ink-jet printing and slit coating, and annealing to obtain a Perovskite (PVK) film;
4) Taking a proper amount of Ethyl Thioglycolate (ET), using Isopropanol (IPA) as a solvent, preparing an ethyl thioglycolate/isopropanol solution, heating and stirring, cooling to room temperature, depositing the ethyl thioglycolate/isopropanol solution on the surface of the perovskite film obtained in the step 2) in a spin coating mode, and annealing to obtain the perovskite film treated by the ethyl thioglycolate/isopropanol;
5) Depositing a charge transport layer and a hole blocking layer on the treated perovskite thin film obtained in the step 3);
6) Depositing a metal electrode on the surface of the film obtained in the step 5) to obtain the perovskite solar cell device treated by ethyl thioglycolate/isopropanol.
Further, the transparent conductive substrate in the step 1) is Glass/ITO, glass/FTO, PEN/ITO, PET/ITO, graphene, metal nanowires, carbon nanotubes, conductive polymers, silver, copper or aluminum thin films.
Further, after the perovskite precursor solution is deposited on the surface of the film in the step 3), annealing treatment is carried out for 10-15 minutes at the temperature of 100-150 ℃, and the perovskite film is obtained.
Further, the concentration of ethyl thioglycolate in the ethyl thioglycolate/isopropanol solution in step 4) was 3.0 mg/ml.
Further, the annealing temperature in the step 4) is 100-150 ℃ and the time is 5-10 minutes, and secondary annealing (on the premise of functional molecule treatment) is helpful for perovskite grain growth.
Further, the charge transport layer in step 5) is PTAA, niOX, tiO 2 、SnO 2 、ZnO 2 、C 60 、C 70 、PC 61 One or more composite films in the BM.
Further, the metal electrode in step 6) is a composite electrode of one or more of Ag, au and Cu.
The invention has the beneficial effects that:
by introducing ET molecules on the surface of the perovskite and utilizing a secondary annealing mode, the perovskite thin film with large grain size, high quality and few crystal boundaries (namely few defect sites) is obtained; meanwhile, due to the action of sulfydryl and carbonyl in ET molecules, the ET can effectively passivate defect points, namely uncoordinated lead ions, on the surface of the perovskite thin film, so that the secondary passivation effect is achieved, the purpose of improving the performance of the thin film is further achieved, and the optimization of the performance of the perovskite solar cell is facilitated.
Drawings
FIG. 1 is an SEM image of perovskite thin films before and after ET/IPA treatment.
FIG. 2 is a statistical plot of perovskite thin film grain size before and after ET/IPA treatment.
FIG. 3 is an XRD pattern of the perovskite thin film before and after ET/IPA treatment.
FIG. 4 is a graph showing the UV absorption of perovskite thin films before and after ET/IPA treatment.
FIG. 5 is a PL profile of perovskite thin films before and after ET/IPA treatment.
FIG. 6 is a graph of SCLC of perovskite thin films before and after ET/IPA treatment.
FIG. 7 is an XPS plot of perovskite thin films before and after ET/IPA treatment.
FIG. 8 is a DFT calculation chart of lead ion adsorption energy on the surfaces of ET molecules and perovskite thin films.
FIG. 9 is a Raman plot of ET, pbI2 and ET-PbI 2.
FIG. 10 is a JV plot of perovskite solar cells before and after ET/IPA treatment.
FIG. 11 is a graph showing the trend of the stability of perovskite solar cells before and after ET/IPA treatment.
Detailed Description
The invention will be further described with reference to the drawings and examples in the following description, but the scope of the invention is not limited thereto.
Example 1
And (3) preparing a perovskite solar cell based on Glass/ITO/PTAA/PVK/C60/BCP/Ag.
S1, ultrasonically cleaning a Glass/ITO substrate by using deionized water, acetone, ethanol and isopropanol in sequence, drying, treating by using plasma equipment, and taking out for later use.
S2, spin-coating the PTAA solution (2.0 mg/ml, 1ml of toluene) on a Glass/ITO surface (6000 revolutions, 30 seconds), annealing (100 ℃,10 minutes), and cooling to normal temperature to obtain the PTAA film.
S3, weighing PbI 2 (426.4 mg), CsI (52 mg), PbBr 2 (27.5 mg), FAI (137.6 mg), using 1ml of a mixed solution (DMF: DMSO, v = 3) as a solvent, heated at 60 ℃ for 2 hours with stirring, left to room temperature, and then filtered using a polytetrafluoroethylene filter tip having a diameter of 0.22um to obtain a clear bright yellow perovskite precursor solution FA 0.8 Cs 0.2 PbI 2.85 Br 0.15 . And then, taking 70ul of perovskite precursor solution to spin-coat on the surface of the PTAA film, and annealing at 100 ℃ for 10 minutes to obtain the perovskite film.
S4, taking 3mg of ET, using 1ml of IPA as a solvent, preparing an ET/IPA solution with the concentration of 3mg/ml, heating and stirring at 60 ℃ for 10 minutes, and then placing to room temperature. Subsequently, an ET/IPA solution was deposited on the surface of the PVK film obtained in S3 by spin coating, and an ET/IPA treated PVK film was obtained by a secondary annealing (100 ℃,5 minutes).
S5, sequentially carrying out thermal evaporation deposition on an electron transport layer C60 and a hole blocking layer BCP (2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline), wherein the thicknesses are 150 nm and 5 nm respectively, and the deposition rates are 0.01nm/s (the vacuum degree is less than 1 multiplied by 10) -4 bar) and finally depositing a copper metal electrode.
Using the perovskite thin film prepared in the step S3 as a material before ET/IPA treatment, and using the perovskite thin film prepared in the step S4 as a material after treatment
As can be seen from fig. 1 and 2, the crystal grain size of the perovskite thin film after ET/IPA treatment is significantly increased, and the grain boundaries are significantly reduced, so that the defect points at the grain boundaries are relatively reduced. As shown in fig. 3, the ET/IPA treated perovskite thin film has stronger diffraction peaks, indicating that the quality of the thin film is significantly improved compared with that of the untreated perovskite thin film; in addition, as shown in fig. 4, the ultraviolet absorption intensity of the ET/IPA treated perovskite thin film is slightly increased, and the effect of improving the quality of the perovskite thin film after the ET/IPA treatment is verified again. As can be seen from PL test results, as shown in FIG. 5, the ET/IPA treated perovskite thin film has lower fluorescence intensity, which indicates that the non-radiative recombination phenomenon of the ET/IPA treated perovskite thin film is significantly reduced, and is beneficial to efficient carrier transmission. After testing by SCLC characterization (see FIG. 6), the ET/IPA treated perovskite has a lower V TFL This indicates that the treated perovskite thin film has a smaller defect state density, and the effect of reducing the non-radiative recombination phenomenon after ET/IPA treatment is verified again. From fig. 1 we know that grain boundary reduction may be one of the causes of non-radiative recombination reduction, and to verify the passivating effect of thiol and carbonyl groups in ET molecules (i.e. binding with non-coordinated lead ions present at the perovskite surface), it was demonstrated by relevant tests. As shown in fig. 7, from the XPS test results, it was found that the XPS signal position of the lead ions on the surface of the ET/IPA-treated perovskite thin film was changed, and it was confirmed that the ET molecules could bind to the lead ions that were not coordinated to the perovskite surface. As shown by DFT theoretical calculation (as shown in FIG. 8), ETThe adsorption energy of the sulfydryl, carbonyl and lead ions in the molecule is-0.3 eV and-0.28 eV respectively, (which represents the adsorption energy, and represents that a sulfur atom in the sulfydryl and an oxygen atom in the carbonyl can be combined with lead ions on the surface of the perovskite because of the negative value), which indicates that both the sulfydryl and the carbonyl in the ET molecule can be combined with the lead ions, and indicates that the sulfydryl is more easily combined with the lead ions than the carbonyl due to the lower adsorption energy of the sulfydryl and the lead ions. In order to further verify that both sulfydryl and carbonyl in an ET molecule can be combined with lead ions, an ET-PbI2 complex is obtained after the ET and PbI2 are mixed, and Raman tests show that compared with Raman signals of the ET-PbI2 and signals of the ET and PbI2, signals of the sulfydryl and the carbonyl are shifted compared with those of the ET-PbI2, so that both the sulfydryl and the carbonyl in the ET molecule can be effectively combined with the lead ions. As can be seen from the JV test results, the device after ET/IPA treatment has higher photoelectric conversion efficiency as shown in FIG. 10; meanwhile, the processed device has longer-term stability through stability tests (as shown in fig. 11). The improvement on the photoelectric conversion efficiency and the stability can be attributed to the reduction of the surface defect state of the perovskite thin film and the improvement of the quality of crystal grains.
Claims (7)
1. A method for improving the performance of a perovskite solar cell through secondary growth of perovskite crystal grains is characterized by comprising the following specific operations:
1) Sequentially cleaning a transparent conductive substrate by using deionized water, acetone, ethanol and isopropanol, drying the cleaned substrate, treating by using plasma equipment, and standing at normal temperature for later use;
2) Spin coating a layer of film on the surface of the substrate, wherein the film is PTAA, PEDOT, PSS, niOX and TiO 2 、SnO 2 、ZnO 2 、C 60 、C 70 、PC 61 One or more composite films in the BM;
3) Weighing PbI 2 、PbBr 2 CsI, csBr and FAI, and preparing a perovskite precursor solution, wherein the perovskite precursor solution is FA 0.8 Cs 0.2 PbI 2.85 Br 0.15 The perovskite precursor solution is subjected to spin coating, blade coating and ink jetDepositing the film surface obtained in the step 2) in one or more modes of printing and slit coating, and annealing to obtain a perovskite film;
4) Taking a proper amount of ethyl thioglycolate, using isopropanol as a solvent, preparing an ethyl thioglycolate/isopropanol solution, heating, stirring, cooling to room temperature, depositing the ethyl thioglycolate/isopropanol solution on the surface of the perovskite film obtained in the step 2) in a spin coating mode, and annealing to obtain the perovskite film treated by the ethyl thioglycolate/isopropanol;
5) Depositing a charge transport layer and a hole blocking layer on the treated perovskite thin film obtained in the step 4);
6) Depositing a metal electrode on the surface of the film obtained in the step 5) to obtain the perovskite solar cell device treated by ethyl thioglycolate/isopropanol.
2. The method of claim 1, wherein the transparent conductive substrate in step 1) is Glass/ITO, glass/FTO, PEN/ITO, PET/ITO, graphene, metal nanowires, carbon nanotubes, conductive polymers, silver, copper, or aluminum thin films.
3. The method according to claim 1, wherein the perovskite precursor solution is deposited on the surface of the thin film in step 3), and then the thin film is annealed at 100-150 ℃ for 10-15 minutes to obtain the perovskite thin film.
4. The method of claim 1, wherein the concentration of ethyl thioglycolate in the ethyl thioglycolate/isopropanol solution in step 4) is 1.0 to 10.0 mg/ml.
5. The method of claim 1, wherein the annealing in step 4) is carried out at a temperature of 100 to 150 ℃ for a time of 5 to 10 minutes.
6. The method according to claim 1, wherein the charge transport layer in step 5) is PTAA, niOX, tiO 2 、SnO 2 、ZnO 2 、C 60 、C 70 、PC 61 One or more composite films in the BM.
7. The method according to claim 1, wherein the metal electrode in step 6) is a composite electrode of one or more of Ag, au and Cu.
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| CN116535969A (en) * | 2023-05-06 | 2023-08-04 | 广汽本田汽车有限公司 | Novel IPA pretreatment solvent and preparation method thereof |
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