CN112864329A - Perovskite solar cell and preparation method thereof - Google Patents
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Abstract
The invention provides a perovskite solar cell and a preparation method thereof. The preparation method comprises the following steps: mixing an additive and a perovskite material solution to prepare a precursor mixed solution; the additive is 4,4' -bipyridyl; spin-coating the precursor mixed solution on a conductive glass substrate with an electron transport layer to form a film, and annealing to form a crystalline perovskite thin film; coating a mixed solution containing a hole transport material on the perovskite thin film to form a hole transport layer; and evaporating a metal film on the hole transport layer to be used as a back electrode to obtain the perovskite solar cell. The perovskite solar cell containing the specific additive has excellent photoelectric conversion rate and stability.
Description
Technical Field
The invention relates to a solar cell, in particular to a perovskite solar cell, and belongs to the technical field of solar cells.
Background
Over the last decade, organic-inorganic hybrid perovskite materials have a high optical absorption coefficient (10)5cm-1) Large electron/hole diffusion length (up to 1 μm), easy band gap adjustment (1-2.5eV), small exciton binding energy (about 40meV), low cost solution processing, etc., allowing rapid development of polycrystalline perovskite solar cells. Currently, the photoelectric conversion efficiency of polycrystalline perovskite solar cells exceeds 25%, and is widely regarded by various countries and the field of solar cells.
During solution preparation of polycrystalline perovskite thin films, commonly used solution processing and annealing techniques can lead to disorder of partial structure, volatilization of components, and degradation of photoactive layers, thereby producing uncomplexed lead ions (Pb)2+) And lead clusters (Pb clusters) (chem.soc.rev.2019,48,3842). The migration of some halogen ions and the rapid film crystallization mode can cause problems such as vacancy and interstitial defects, voids and pinholes. The final perovskite thin film has significant internal and surface defects that result in more non-radiative recombination centers and energy loss, which severely affect device efficiency (Science 2017,355,722; Science,2019,364,833; adv.mater.2015, 27, 1837). Therefore, high quality perovskite thin films directly determine the performance of polycrystalline perovskite cells.
Additive engineering is an effective method for preparing high quality perovskite thin films (adv. energy mater.2019, 1902579). Han et al added urea to the perovskite solution to adjust the crystal growth and morphology and prepare a high quality, large size perovskite thin film (Solar RRL 2018,2, 1800054). Jen et al added DIO additive to the precursor fluid to obtain a composition with high crystallinity and good surface propertiesSurface homogeneous perovskite thin films (adv. mater.,2014,26, 3748). Recently, new molecular additives such as NH have been developed through molecular design2-R-NH2And the coexisting structure of N-H and C ═ O can effectively achieve defect passivation of the perovskite thin film (sci.adv.2019,5, eaav 8925; Science 2019,366,1509).
However, most current molecular additives contain longer alkyl chains, and their insulating properties are not favorable for maintaining and improving the carrier mobility of the perovskite thin film. Therefore, finding a functionalized molecular additive from the aspect of finding a unique molecular structure can enhance the carrier mobility of the perovskite thin film while effectively passivating the defects of the perovskite thin film, so as to promote the improvement of the photoelectric property of the device, and still has great challenges.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a perovskite solar cell having high photoelectric conversion efficiency and device stability, and a method for manufacturing the same.
In order to achieve the above object, the present invention provides a method for manufacturing a perovskite solar cell, the method comprising the steps of:
mixing an additive and a perovskite material solution to prepare a precursor mixed solution; wherein the additive is 4,4' -bipyridine;
spin-coating the precursor mixed solution on a conductive glass substrate with an electron transport layer to form a film, and annealing to form a crystalline perovskite thin film;
coating a mixed solution containing a hole transport material on the perovskite thin film to form a hole transport layer;
and evaporating a metal film on the hole transport layer to be used as a back electrode to obtain the perovskite solar cell.
In the perovskite solar cell, 4,4 '-bipyridyl is used as an additive, and the chemical structure of the 4,4' -bipyridyl (BPY [4,4]) is as follows:
the pyridine ring is of a symmetrical structure formed by connecting two pyridine rings through a para-position structure, the left end and the right end are N atoms, and the two pyridine rings are of a conjugated structure.
In the perovskite solar cell, 4' -bipyridyl is used as an additive, two pyridine rings are connected in a symmetrical and conjugated way through the unique chemical molecular structure of the additive, and the N atoms of the pyridine at the left and right ends can be well connected with the unliganded Pb in the perovskite thin film2+The effective defect passivation is realized by coordination, and the conjugated performance of the 4,4' -bipyridyl is connected with the crystal boundary of the perovskite, so that the function of enhancing the carrier mobility is realized. 4,4' -dipyridyl is also beneficial to controlling the appearance of the growth of the perovskite film and preparing larger grain size; pyridine N and Pb simultaneously2+The prepared perovskite film has good fluorescence property due to coordination and passivation; the hydrophobic property of the 4,4' -bipyridyl can effectively prevent water and oxygen from damaging the perovskite film, so that the more stable perovskite film is obtained; finally, the photoelectric efficiency and the device stability of the perovskite solar cell containing the additive are improved.
In one embodiment of the invention, the molar ratio of the additive to the Pb atoms in the perovskite material solution is from 0.05 to 5: 100.
in one embodiment of the invention, the perovskite material solution solute employed comprises MAPbI3、MAPb(I,Br)3Or (FAMA) Pb (I, Br)3. The method specifically comprises the following steps: MAPbi3：methyl ammonium lead iodide，CH3NH3PbI3；MAPb(I,Br)3)：methyl ammonium lead iodide/bromide；(FAMA)Pb(I,Br)3: formaminium/methyl ammonium lead iodide/bromide. The perovskite material solution is prepared by mixing the following solvents in a volume ratio of 4:1, a mixed solvent of DMF and DMSO.
In one embodiment of the present invention, the annealing temperature is 100 ℃ to 150 ℃ and the annealing time is 10 minutes to 15 minutes.
In one embodiment of the present invention, the mixed solution containing the hole transport material is a Spiro-OMeTAD solution. Wherein the solution of Spiro-OMeTAD is prepared by dissolving lithium bis (trifluoromethane sulfonyl) imide in acetonitrile, Spiro-OMeTAD (available from market) and 4-tert-butylpyridine in chlorobenzene.
In a further embodiment of the present invention, the Spiro-OMeTAD solution is prepared by the following steps:
dissolving 500-530 mg of lithium bis (trifluoromethanesulfonyl) imide in 1-2 mL of acetonitrile solution to form an acetonitrile solution of Li-TFSI;
15 to 25 μ L of an acetonitrile solution of Li-TFSI, 80 to 90mg of Spiro-OMeTAD and 28 μ L of 4-tert-butylpyridine were co-dissolved in 1 to 2mL of chlorobenzene to obtain a mixed solution containing a hole-transporting material.
The method comprises the following steps: 520mg of lithium bistrifluoromethanesulfonylimide (LiTFSI) was dissolved in 1mL of acetonitrile to form an acetonitrile solution of Li-TFSI, and then 20. mu.L of the acetonitrile solution of Li-TFSI, 85mg of Spiro-OMeTAD (2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene) and 28. mu.L of 4-t-butylpyridine were co-dissolved in 1mL of chlorobenzene to obtain a mixed solution containing a hole transport material.
In one embodiment of the present invention, the metal thin film is an Au metal thin film; wherein the thickness of the metal film is 80-120 nm.
In one embodiment of the present invention, the electron transport layer is TiO2An electron transport layer.
The invention also provides a perovskite solar cell which is prepared by the preparation method of the perovskite solar cell.
The perovskite solar cell containing the specific additive has excellent photoelectric conversion efficiency and stability.
Drawings
FIG. 1 is a chemical structural formula of an additive for perovskite solar cell of the present invention and an additive in comparative example.
FIG. 2 is a graph of the UV absorption spectra of perovskite thin films of the present invention based on different concentrations of 4,4' -bipyridine additive (comparative example 4 and examples 2-6): the concentration ranges from 0 to 5 mol%.
FIG. 3 is a fluorescence spectrum of the perovskite thin films of comparative example 4 and examples 2 to 6 of the present invention (the substrate is glass, and the excitation wavelength is 690 nm).
FIG. 4 shows a FTO/TiO structure of a pure electronic device prepared by the present invention2Defect state density and carrier mobility for the/perovskite thin film/PCBM/Ag (a and c) and pure hole device FTO/PEDOT PSS/perovskite thin film/P3 HT/Ag (b and d) tests: (a, c) are the perovskite thin film prepared in comparative example 4; (b, d) are the perovskite thin film prepared in example 3.
FIG. 5 is a scanning electron microscope top view of a perovskite thin film prepared by the invention: (a) was prepared in comparative example 4; (b) containing the compound obtained in example 2; (c) counting the size of crystal grains; (d) x-ray diffraction pattern.
FIG. 6 is a contact angle test chart of perovskite thin film prepared by the present invention: (a) prepared in comparative example 4, (b) prepared in example 5.
Fig. 7 is a current-voltage plot of a perovskite cell prepared according to the present invention: the reference was made to the cell of comparative example 4, the others being the cells of example 3 and comparative examples 5 to 7 containing 0.5 mol% of the other additives, respectively.
Fig. 8 is a graph of the stability of perovskite cells prepared according to the present invention: (a) comparative example 4, (b) example 5.
Detailed Description
Example 1
This example provides a compound 4,4' -bipyridine (BPY 4, 4) for use as an additive in perovskite solar cells, having a structural formula shown in FIG. 1, wherein the structural formula is:
example 2
The embodiment provides a preparation process of a polycrystalline perovskite thin film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by using ultrasonic waves, and then treating for 15 minutes by using ozone; it was immersed in 40mM TiCl at 70 deg.C4Keeping the temperature in the aqueous solution for 30min, thereby forming a layer of compact TiO on the surface of the FTO conductive glass2Film for subsequent removal of FTO conductive glassAnd washing with ethanol, and naturally drying. Taking additive 4,4' -dipyridyl and perovskite material (MAPbI)3) The solutions were mixed to prepare a precursor mixed solution (solvent DMF/DMSO in a volume ratio of 4: 1; the molar ratio of the additive 4-cyanopyridine to Pb was 0.1: 100) (ii) a Dropping the precursor solution on TiO2And spin-coating the layer at 4000 rpm for 60 seconds, dripping 130 mu L of chlorobenzene solution when the spin-coating is carried out for 40 seconds, and heating at 100 ℃ and 150 ℃ for 10-15min to obtain the perovskite light absorption layer film.
Dissolving 520mg of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 1mL of acetonitrile solution; then 20 mu L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28 mu L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the obtained hole transport layer Spiro-OMeTAD; dropping the perovskite thin film on the perovskite thin film, spin-coating for 30-50s at the speed of 2000-. And finally, continuously evaporating and plating an Au metal film with the thickness of 80-120nm on the hole transport layer to be used as a back electrode, and obtaining the perovskite solar cell.
Example 3
The embodiment provides a preparation process of a polycrystalline perovskite thin film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by using ultrasonic waves, and then treating for 15 minutes by using ozone; it was immersed in 40mM TiCl at 70 ℃4Keeping the temperature in the aqueous solution for 30min, thereby forming a layer of compact TiO on the surface of the FTO conductive glass2And (4) taking out the FTO conductive glass, washing with ethanol, and naturally airing. Taking additive 4,4' -dipyridyl and perovskite material (MAPbI)3) The solutions were mixed to prepare a precursor mixed solution (solvent DMF/DMSO in a volume ratio of 4: 1; molar ratio of additive 4-cyanopyridine to Pb 0.5:100) (ii) a Dropping the precursor solution on TiO2And spin-coating the layer for 60 seconds at the speed of 4000 revolutions per minute, dropwise adding 130 mu L of chlorobenzene solution when the spin-coating is carried out for 40 seconds, and heating at the temperature of 100-150 ℃ for 10-15min to obtain the perovskite light absorption layer film.
Dissolving 520mg of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 1mL of acetonitrile solution; then 20 mu L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28 mu L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene to prepare a mixed solution of the obtained hole transport layer Spiro-OMeTAD; dropping it on perovskite film, spin-coating at 2000-5000rpm for 30-50s, and placing in air for 12 hr. And finally, continuously evaporating and plating an Au metal film with the thickness of 80-120nm on the hole transport layer to be used as a back electrode, and obtaining the perovskite solar cell.
Example 4
The embodiment provides a preparation process of a polycrystalline perovskite thin film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by using ultrasonic waves, and then treating for 15 minutes by using ozone; it was immersed in 40mM TiCl at 70 ℃4Keeping the temperature in the aqueous solution for 30min, thereby forming a layer of compact TiO on the surface of the FTO conductive glass2And (4) taking out the FTO conductive glass, washing with ethanol, and naturally airing. Taking additive 4,4' -dipyridyl and perovskite material (MAPbI)3) The solutions were mixed to prepare a precursor mixed solution (solvent DMF/DMSO in a volume ratio of 4: 1; molar ratio of additive 4-cyanopyridine to Pb 1: 100) (ii) a Dropping the precursor solution on TiO2And spin-coating the layer at 4000 rpm for 60 seconds, dripping 130 mu L of chlorobenzene solution when the spin-coating is carried out for 40 seconds, and heating at 100 ℃ and 150 ℃ for 10-15min to obtain the perovskite light absorption layer film.
Dissolving 520mg of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 1mL of acetonitrile solution; then 20 mu L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28 mu L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the obtained hole transport layer Spiro-OMeTAD; dropping it on perovskite film, spin-coating at 2000-5000rpm for 30-50s, and placing in air for 12 hr. And finally, continuously evaporating and plating an Au metal film with the thickness of 80-120nm on the hole transport layer to be used as a back electrode, and obtaining the perovskite solar cell.
Example 5
The embodiment provides a preparation process of a polycrystalline perovskite thin film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by using ultrasonic waves, and then treating for 15 minutes by using ozone; it was immersed in 40mM TiCl at 70 ℃4Maintaining in the aqueous solution for 30min to obtain a solutionA layer of compact TiO is formed on the surface of the FTO conductive glass2And (4) taking out the FTO conductive glass, washing with ethanol, and naturally airing. Taking additive 4,4' -dipyridyl and perovskite material (MAPbI)3) The solutions were mixed to prepare a precursor mixed solution (solvent DMF/DMSO in a volume ratio of 4: 1; molar ratio of additive 4-cyanopyridine to Pb 3: 100) (ii) a Dropping the precursor solution on TiO2And spin-coating the layer at 4000 rpm for 60 seconds, dripping 130 mu L of chlorobenzene solution when the spin-coating is carried out for 40 seconds, and heating at 100 ℃ and 150 ℃ for 10-15min to obtain the perovskite light absorption layer film.
Dissolving 520mg of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 1mL of acetonitrile solution; then 20 mu L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28 mu L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene to prepare a mixed solution of the obtained hole transport layer Spiro-OMeTAD; dropping it on perovskite film, spin-coating at 2000-5000rpm for 30-50s, and placing in air for 12 hr. And finally, continuously evaporating and plating an Au metal film with the thickness of 80-120nm on the hole transport layer to be used as a back electrode, and obtaining the perovskite solar cell.
Example 6
The embodiment provides a preparation process of a polycrystalline perovskite thin film and a battery, which comprises the following specific steps:
cleaning FTO conductive glass by using ultrasonic waves, and then treating for 15 minutes by using ozone; it was immersed in 40mM TiCl at 70 ℃4Keeping the temperature in the aqueous solution for 30min, thereby forming a layer of compact TiO on the surface of the FTO conductive glass2And (4) taking out the FTO conductive glass, washing with ethanol, and naturally airing. Taking additive 4,4' -dipyridyl and perovskite material (MAPbI)3) The solutions were mixed to prepare a precursor mixed solution (solvent DMF/DMSO in a volume ratio of 4: 1; molar ratio of additive 4-cyanopyridine to Pb 5:100) (ii) a Dropping the precursor solution on TiO2And spin-coating the layer at 4000 rpm for 60 seconds, dripping 130 mu L of chlorobenzene solution when the spin-coating is carried out for 40 seconds, and heating at 100 ℃ and 150 ℃ for 10-15min to obtain the perovskite light absorption layer film.
Dissolving 520mg of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 1mL of acetonitrile solution; then 20 mu L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28 mu L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the obtained hole transport layer Spiro-OMeTAD; dropping it on perovskite film, spin-coating at 2000-5000rpm for 30-50s, and placing in air for 12 hr. And finally, continuously evaporating and plating an Au metal film with the thickness of 80-120nm on the hole transport layer to be used as a back electrode, and obtaining the perovskite solar cell.
Comparative example 1
This example provides a compound 2,2' -bipyridine (BPY 2, 2) for use as an additive in perovskite solar cells, having the formula:
comparative example 2
The present example provides an additive for perovskite solar cells, which is a compound of tert-butylpyridine (TBP), and has the structural formula:
comparative example 3
This example provides a comparative compound, 4-Cyanopyridine (CNP), for use as an additive in perovskite solar cells, having the formula:
comparative example 4
This example provides a comparative process for preparing a polycrystalline perovskite thin film and a battery, comprising the steps of:
cleaning FTO conductive glass by using ultrasonic waves, and then treating for 15 minutes by using ozone; it was immersed in 40mM TiCl at 70 ℃4Keeping the temperature in the aqueous solution for 30min, thereby forming a layer of compact TiO on the surface of the FTO conductive glass2And (4) taking out the FTO conductive glass, washing with ethanol, and naturally airing. Taking perovskite material (MAPbI3) Dripping the precursor solution (solvent DMF/DMSO according to the volume ratio of 4:1) solution into TiO2And spin-coating the layer at 4000 rpm for 60 seconds, dripping 130 mu L of chlorobenzene solution when the spin-coating is carried out for 40 seconds, and heating at 100 ℃ and 150 ℃ for 10-15min to obtain the perovskite light absorption layer film.
Dissolving 520mg of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 1mL of acetonitrile solution; then 20 mu L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28 mu L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene to prepare a mixed solution of the obtained hole transport layer Spiro-OMeTAD; dropping it on perovskite film, spin-coating at 2000-5000rpm for 30-50s, and placing in air for 12 hr. And finally, continuously evaporating and plating an Au metal film with the thickness of 80-120nm on the hole transport layer to be used as a back electrode, and obtaining the perovskite solar cell.
Comparative example 5
This example provides a comparative process for preparing a polycrystalline perovskite thin film and a battery, comprising the steps of:
cleaning FTO conductive glass by using ultrasonic waves, and then treating for 15 minutes by using ozone; it was immersed in 40mM TiCl at 70 deg.C4Keeping the temperature in the aqueous solution for 30min, thereby forming a layer of compact TiO on the surface of the FTO conductive glass2And (4) taking out the FTO conductive glass, washing with ethanol, and naturally airing. Mixing the additive with perovskite material (MAPbI)3) The solutions were mixed to prepare a precursor mixed solution (solvent DMF/DMSO in a volume ratio of 4: 1; the molar ratio of the additive 2,2' -bipyridyl to Pb was 0.5:100) (ii) a Dropping the precursor solution on TiO2And spin-coating the layer at 4000 rpm for 60 seconds, dripping 130 mu L of chlorobenzene solution when the spin-coating is carried out for 40 seconds, and heating at 100 ℃ and 150 ℃ for 10-15min to obtain the perovskite light absorption layer film.
Dissolving 520mg of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 1mL of acetonitrile solution; then 20 mu L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28 mu L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the obtained hole transport layer Spiro-OMeTAD; dropping it on perovskite film, spin-coating at 2000-5000rpm for 30-50s, and placing in air for 12 hr. And finally, continuously evaporating and plating an Au metal film with the thickness of 80-120nm on the hole transport layer to be used as a back electrode, and obtaining the perovskite solar cell.
Comparative example 6
This example provides a comparative process for preparing a polycrystalline perovskite thin film and a battery, comprising the steps of:
cleaning FTO conductive glass by using ultrasonic waves, and then treating for 15 minutes by using ozone; it was immersed in 40mM TiCl at 70 ℃4Keeping the temperature in the aqueous solution for 30min, thereby forming a layer of compact TiO on the surface of the FTO conductive glass2And (4) taking out the FTO conductive glass, washing with ethanol, and naturally airing. Mixing the additive with perovskite material (MAPbI)3) The solutions were mixed to prepare a precursor mixed solution (solvent DMF/DMSO in a volume ratio of 4: 1; the molar ratio of the additive tert-butylpyridine to Pb is 0.5:100) (ii) a Dropping the precursor solution on TiO2And spin-coating the layer at 4000 rpm for 60 seconds, dripping 130 mu L of chlorobenzene solution when the spin-coating is carried out for 40 seconds, and heating at 100 ℃ and 150 ℃ for 10-15min to obtain the perovskite light absorption layer film.
Dissolving 520mg of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 1mL of acetonitrile solution; then 20 mu L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28 mu L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene together to prepare a mixed solution of the obtained hole transport layer Spiro-OMeTAD; dropping it on perovskite film, spin-coating at 2000-5000rpm for 30-50s, and placing in air for 12 hr. And finally, continuously evaporating and plating an Au metal film with the thickness of 80-120nm on the hole transport layer to be used as a back electrode, and obtaining the perovskite solar cell.
Comparative example 7
This example provides a comparative process for preparing a polycrystalline perovskite thin film and a battery, comprising the steps of:
cleaning FTO conductive glass by using ultrasonic waves, and then treating for 15 minutes by using ozone; it was immersed in 40mM TiCl at 70 ℃4Keeping the temperature in the aqueous solution for 30min, thereby forming a layer of compact TiO on the surface of the FTO conductive glass2And (4) taking out the FTO conductive glass, washing with ethanol, and naturally airing. Mixing the additive with perovskite material (MAPbI)3) SolutionMixing the solution to prepare a precursor mixed solution (the solvent DMF/DMSO is 4:1 in volume ratio, and the molar ratio of the additive 4-cyanopyridine to Pb is 0.5: 100); dropping the precursor solution on TiO2And spin-coating the layer at 4000 rpm for 60 seconds, dripping 130 mu L of chlorobenzene solution when the spin-coating is carried out for 40 seconds, and heating at 100 ℃ and 150 ℃ for 10-15min to obtain the perovskite light absorption layer film.
Dissolving 520mg of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 1mL of acetonitrile solution; then 20 mu L of acetonitrile solution containing Li-TFSI, 85mg of Spiro-OMeTAD and 28 mu L of 4-tert-butylpyridine are dissolved in 1mL of chlorobenzene to prepare a mixed solution of the obtained hole transport layer Spiro-OMeTAD; dropping it on perovskite film, spin-coating at 2000-5000rpm for 30-50s, and placing in air for 12 hr. And finally, continuously evaporating and plating an Au metal film with the thickness of 80-120nm on the hole transport layer to be used as a back electrode, and obtaining the perovskite solar cell.
Comparative Experimental example 1
This example provides a method of fabricating a perovskite solar cell, reference (j. mater. chem.a,2019,7,4977), using 2,2' -bipyridine as an additive (1.0 wt%) incorporated into a perovskite material FA0.88Cs0.12PbI3And manufacturing the perovskite light absorption layer film. Simulating sunlight at 25 deg.c with xenon lamp in light intensity of 100mW/cm2Under the condition, the battery (effective area 0.0725 cm)2) The optoelectronic parameters are shown in the appendix (Table 1).
Comparative Experimental example 2
This example provides a method of fabricating a perovskite solar cell, reference (j. mater. chem.a,2015,3,22191) using only the perovskite material MAPbI3And manufacturing the perovskite light absorption layer film. Simulating sunlight at 25 deg.c with xenon lamp in light intensity of 100mW/cm2Under the condition, the battery (effective area 0.0725 cm)2) The optoelectronic parameters are shown in the appendix (Table 1).
The parameters of the solar cell performance can be obtained by photoelectric performance test (at 25 ℃, a xenon lamp is used for simulating sunlight, and the light intensity is 100mW/cm2The test was carried out under the conditions (effective area 0.0725 cm)2) See table 1).
TABLE 1 test Table for perovskite solar cells prepared in examples 2-6 and comparative examples 4-7
FIG. 2 is a graph of the UV absorption spectra of perovskite thin films based on different concentrations of 4,4' -bipyridine additive (comparative example 4 and examples 2-6): the concentration ranges from 0 to 5 mol%. As can be seen from fig. 2, the increase in absorbance of the perovskite thin film based on 4,4' -bipyridine is beneficial to the increase in short-circuit current of the corresponding device.
Perovskite solar cell additives based on 4,4' -bipyridine in the above examples (example 3) were selected to fabricate perovskite thin films and perovskite solar cells, and compared to those in comparative example 4. The results show that the increase in fluorescence intensity after the addition of 4,4' -bipyridine also means a decrease in internal defects of the perovskite thin film (see fig. 3); the 4,4' -bipyridine additive reduces defect state density and enhances the enhancement of electron and hole mobility of the perovskite thin film (see fig. 4); the 4,4' -bipyridine additive promotes the growth of perovskite thin films, resulting in higher-quality, larger-sized grains (see fig. 5); contact angle tests are compared, and the perovskite thin film after 4,4' -bipyridyl is added has a larger contact angle (see fig. 6), and can better prevent water and oxygen (the bipyridyl ring has better hydrophobicity) from entering into a grain boundary to damage the perovskite thin film. For the above reasons, the 4,4' -bipyridine additive can enhance the photoelectric conversion efficiency (see fig. 7) and stability (see fig. 8) of the perovskite solar cell device. The perovskite thin film and the cell using the additives 2,2' -bipyridine (comparative example 5) and t-butylpyridine (comparative example 6) of the other examples also had better cell efficiency than comparative example 4 (see table 1).
Compared with comparative experimental examples 1 and 2, the perovskite solar cell added with 4,4' -bipyridine also has higher photoelectric conversion efficiency, see table 1 (the test results of other partial examples are also better than those in comparative experimental examples 1 and 2). It can be seen that the perovskite solar cell based on the additive of the present embodiment is compared to the perovskite solar cell based on other types of additivesThe perovskite solar cell has better cell performance; this is because the unique chemical molecular structure of 4,4' -bipyridine makes two pyridine rings symmetrically and conjugated, and the pyridine N atoms at the left and right ends can be well coordinated with Pb in the perovskite film2+The effective defect passivation is realized by coordination, and the conjugated performance of the 4,4' -bipyridyl is connected with the crystal boundary of the perovskite, so that the function of enhancing the carrier mobility is realized. 4,4' -bipyridine is also beneficial to controlling the appearance of the growth of the perovskite film and preparing larger grain size; pyridine N and Pb simultaneously2+The prepared perovskite film has good fluorescence property due to coordination and passivation; finally, the photoelectric efficiency of the perovskite solar cell using the additive is improved.
Table 2 perovskite solar cell test table prepared by additive and different perovskite materials in example 3
The perovskite solar cell additive based on 4,4' -bipyridine in example 3 was also mixed with different perovskite materials in a ratio (0.5:100) to prepare a perovskite solar cell as described above. The parameters of the solar cell performance can be obtained by photoelectric performance test (at 25 ℃, a xenon lamp is used for simulating sunlight, and the light intensity is 100mW/cm2The test was carried out under the conditions (effective area 0.0725 cm)2) See table 2).
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a perovskite solar cell comprises the following steps:
mixing an additive and a perovskite material solution to prepare a precursor mixed solution; wherein the additive is 4,4' -bipyridine;
spin-coating the precursor mixed solution on a conductive glass substrate with an electron transport layer to form a film, and annealing to form a crystalline perovskite thin film;
coating a mixed solution containing a hole transport material on the perovskite thin film to form a hole transport layer;
and evaporating a metal thin film on the hole transport layer to be used as a back electrode, so as to obtain the perovskite solar cell.
2. The production method according to claim 1, wherein the molar ratio of the additive to Pb atoms in the perovskite material solution is 0.05 to 5: 100.
3. the production method according to claim 1, wherein the solute of the perovskite material solution comprises MAPbI3、MAPb(I,Br)3Or (FAMA) Pb (I, Br)3；
Preferably, the solvent of the perovskite material solution is a solvent having a volume ratio of 4:1, a mixed solvent of DMF and DMSO.
4. The method of claim 1, wherein the annealing temperature is 100 ℃ to 150 ℃ and the annealing time is 10 minutes to 15 minutes.
5. The production method according to claim 1, wherein the mixed solution containing a hole transport material is a Spiro-OMeTAD solution.
6. The process according to claim 5, wherein the solution of Spiro-OMeTAD is prepared by co-dissolving lithium bistrifluoromethanesulfonylimide in acetonitrile, Spiro-OMeTAD and 4-tert-butylpyridine in chlorobenzene.
7. The method of claim 6, wherein the Spiro-OMeTAD solution is prepared by:
dissolving 500-530 mg of lithium bis (trifluoromethanesulfonyl) imide in 1-2 mL of acetonitrile solution to form an acetonitrile solution of Li-TFSI;
15 to 25 μ L of an acetonitrile solution of Li-TFSI, 80 to 90mg of Spiro-OMeTAD and 28 μ L of 4-tert-butylpyridine were co-dissolved in 1 to 2mL of chlorobenzene to obtain a mixed solution containing a hole-transporting material.
8. The production method according to claim 1, wherein the metal thin film is an Au metal thin film; the thickness of the metal film is 80nm-120 nm.
9. The production method according to claim 1, wherein the electron transport layer is TiO2An electron transport layer.
10. A perovskite solar cell produced by the method for producing a perovskite solar cell according to any one of claims 1 to 9.
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